JP6457860B2 - Optical three-dimensional resin composition - Google Patents

Description

  The present invention has a high heat distortion temperature and excellent heat resistance, and further, heat treatment is performed after stereolithography to further increase the heat distortion temperature and further improve the heat resistance, while lowering the yellowness and increasing the light transmittance. Optics that can produce an optical three-dimensional object that is excellent in color tone and transparency, and excellent in mechanical properties such as impact resistance and breaking strength, smoothly and with high photocuring speed and high modeling accuracy. The present invention relates to a method for producing a three-dimensional model by performing optical three-dimensional modeling using the resin composition for three-dimensional modeling and the resin composition for optical three-dimensional modeling.

In recent years, a method for three-dimensional optical modeling of a liquid photocurable resin composition based on data input to a three-dimensional CAD has achieved good dimensional accuracy without producing a mold or the like. Have been widely adopted.
As a typical example of the optical three-dimensional modeling method, a predetermined thickness is obtained by selectively irradiating an ultraviolet laser controlled by a computer so that a desired pattern is obtained on the liquid surface of the liquid photocurable resin placed in a container. Then, a liquid resin for one layer is supplied onto the cured layer, and similarly cured by irradiation with an ultraviolet laser in the same manner as described above. The method of obtaining a molded article can be mentioned. By this optical three-dimensional modeling method, it is possible to easily manufacture a model having a considerably complicated shape in a relatively short time.

  About resin or resin composition used for optical three-dimensional modeling, it is required that a three-dimensional model can be manufactured in a short modeling time with high curing sensitivity by active energy rays, and it has low viscosity and excellent handleability at the time of modeling. .

In addition, the three-dimensional model obtained by optical modeling using the resin composition for optical three-dimensional modeling is a model for verifying the appearance design of various industrial products during the design, and for checking the functionality of parts. It is widely used as a model, a resin mold for manufacturing a mold, and a base model for manufacturing a mold.
For three-dimensional objects obtained by optical three-dimensional modeling using a resin composition for optical three-dimensional modeling, mechanical strength such as breaking strength is high, excellent toughness, strong and difficult to break It has been demanded.
Furthermore, in recent years, high transparency and an excellent color tone without yellowing are required for a three-dimensional model obtained by optical three-dimensional modeling using a resin composition for optical three-dimensional modeling. For example, in the field of arts and crafts such as models of automobile and motorcycle lens models, restoration of artworks, imitation and contemporary art, and design presentation models of glass-walled buildings, excellent color tone with excellent transparency and no yellowing There has been a demand for a resin composition for optical three-dimensional modeling that gives a three-dimensional modeled object having the following.

Depending on the application, there is a demand for optical three-dimensional modeling that has a high heat distortion temperature and is excellent in heat resistance even for a model. For example, a three-dimensional object obtained by optical three-dimensional modeling of a resin composition for optical three-dimensional modeling is a model for verifying the shape and performance of a tube or component for passing a heat medium or a thermal fluid, a light source, For models that require heat resistance at the same time as evaluating the functions and shapes of engine and motor peripheral parts, etc., they have high heat resistance that does not deform or change even at high temperatures. The model is required to have chemical and physical thermal stability that does not drop and whose toughness and rigidity are difficult to change after heating.
The thermal deformation temperature (at a high load of 1.81 MPa load) of the optical three-dimensional object obtained from the conventional resin composition for optical three-dimensional object formation is generally 50 ° C. or less, and is used in applications requiring high heat resistance. It was difficult to meet the required characteristics.

  In producing a three-dimensional structure having high mechanical strength and excellent toughness, an optical three-dimensional structure resin containing a cationic polymerizable organic compound having an epoxy group and a radical polymerizable organic compound having an unsaturated double bond A resin composition for optical three-dimensional modeling, comprising a composition comprising a flexibility improver (tensile elongation improver) comprising a tetraethylene oxide unit and / or a 2-substituted tetraethylene oxide unit and a polyether having hydroxyl groups at both ends. The thing is proposed (patent document 1). And in this patent document 1, when optical three-dimensional modeling is performed using the resin composition for optical three-dimensional modeling which mix | blended polyether, not only a tensile elongation property will improve but the three-dimensional modeling which is excellent in load flexibility. It is described that an object (three-dimensional modeled object with little decrease in deflection temperature under load) is obtained. However, the present inventors have prepared the resin composition for optical three-dimensional modeling described in Patent Document 1, particularly the resin composition for optical three-dimensional modeling described in Example 1 and Example 10 thereof. When a follow-up experiment was conducted, optical solid modeling was difficult, and even when optical three-dimensional modeling was possible, the resulting three-dimensional model was weak and brittle, load deflection (heat resistance), tensile elongation It was not possible to obtain a practical three-dimensional model having excellent properties and toughness.

In addition, when the present inventors include an oxetane compound and a polyalkylene ether compound in an optical three-dimensional resin composition containing a cationically polymerizable organic compound and a radically polymerizable organic compound, the impact strength is high and the toughness is increased. It was found out that a resin composition for optical three-dimensional modeling which gives a three-dimensional molded product excellent in the above can be obtained, and filed earlier (see Patent Document 2).
The three-dimensional structure obtained by optical modeling of this optical three-dimensional resin composition containing an oxetane compound and a polyalkylene ether has high impact strength and excellent toughness, but exhibits a yellowish color tone, Also, because it has turbidity and the light transmittance is not sufficient, it can be used effectively for applications where color tone and transparency are not a problem, but it is not suitable for applications that require good color tone and excellent transparency. In addition, the heat resistance is insufficient.

Moreover, in order to improve the transparency of the three-dimensional modeled object obtained by stereolithography, cationic polymerization mainly comprising an alicyclic epoxy compound such as 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate. Polyalkylene glycol di (meth) acrylate as a part of the radical polymerizable organic compound in the resin composition for optical three-dimensional modeling containing a polymerizable organic compound, a radical polymerizable organic compound, a cationic polymerization initiator and a radical polymerization initiator It has been proposed to contain (Patent Document 3).
However, a three-dimensional model obtained by optical modeling of the optical three-dimensional model resin composition has low impact strength, inferior toughness and durability, and further has insufficient heat resistance.

Furthermore, the resin composition for radically polymerizable optical three-dimensional modeling mainly composed of urethane (meth) acrylate contains polyalkylene glycol (meth) acrylate as a part of the radical polymerizable organic compound, and is subjected to optical modeling. It has been proposed to improve the impact resistance of the resulting three-dimensional structure (Patent Document 4).
However, since this resin composition for optical three-dimensional modeling contains only a radical polymerizable organic compound as a photopolymerizable component and does not contain a cationic polymerizable organic compound, the dimensional accuracy of a three-dimensional model obtained by optical modeling However, the resin near the surface was not sufficiently cured due to oxygen inhibition, and even if the resin itself had sufficient transparency, optical three-dimensional modeling was performed. The surface of the modeled object has a drawback that it is rough and does not transmit light sufficiently.

  In view of the above, a three-dimensional structure having a high heat distortion temperature, excellent heat resistance, low yellowness, high light transmittance, excellent color tone and transparency, and excellent mechanical properties such as impact resistance and breaking strength. Development of the resin composition for optical three-dimensional modeling which can manufacture a molded article smoothly and with high productivity with a high photocuring speed and high modeling precision is calculated | required.

JP 2003-73457 A JP 2005-15739 A Special table 2004-530773 gazette JP-A-9-194540

The object of the present invention is that the curing sensitivity by active energy rays is high, a three-dimensional shaped article can be produced with high productivity in a short active energy ray irradiation time, low viscosity and excellent handleability at the time of shaping, In addition to the basic physical properties required for optical three-dimensional modeling resin compositions with high resolution and excellent modeling accuracy and dimensional accuracy, it also has a high heat distortion temperature, excellent heat resistance, low yellowness, and light transmission. It is an object to provide a resin composition for optical three-dimensional modeling that provides a three-dimensional molded product having a high rate, excellent color tone and transparency, and excellent mechanical properties such as impact resistance and breaking strength.
An object of the present invention is to provide a method for producing a three-dimensional structure excellent in heat resistance, color tone, transparency and mechanical properties using the above-described resin composition for optical three-dimensional modeling.

  In order to solve the above-mentioned problems, the present inventors have intensively studied. As a result, in the resin composition for optical three-dimensional modeling containing a cationic polymerizable organic compound, a radical polymerizable organic compound, a cationic polymerization initiator, and a radical polymerization initiator, as a part of the cationic polymerizable organic compound, A compound having 3 or more glycidyl etherified phenol groups and polyalkylene glycol diglycidyl ether, and polyalkylene glycol di (meth) acrylate and polyalkylene glycol mono (meth) acrylate as part of the radical polymerizable organic compound The optical three-dimensional modeling resin composition is required for an optical three-dimensional modeling resin composition that has high curing sensitivity by active energy rays, low viscosity, and high resolution during optical three-dimensional modeling. It has the basic physical properties and the light The three-dimensional structure obtained by optical three-dimensional modeling using the three-dimensional three-dimensional resin composition has a high heat distortion temperature, excellent heat resistance, low yellowness, high light transmittance, and color tone and transparency. In addition, it has excellent mechanical properties such as impact resistance and breaking strength. Furthermore, when the three-dimensional structure is heat-treated at a temperature of 50 ° C. or higher, the heat distortion temperature is further increased, and the heat resistance is further increased. The present invention has been completed by finding improvements.

That is, the present invention
(1) (i) A resin composition for optical three-dimensional modeling containing a cationic polymerizable organic compound (A), a radical polymerizable organic compound (B), a cationic polymerization initiator (C) and a radical polymerization initiator (D) Because;
(Ii) containing a compound (A-1) having three or more glycidyl etherified phenol groups as part of the cationically polymerizable organic compound (A);
(Iii) containing polyalkylene glycol diglycidyl ether (A-2) as part of the cationically polymerizable organic compound (A);
(Iv) containing polyalkylene glycol di (meth) acrylate (B-1) as part of the radically polymerizable organic compound (B); and
(V) containing polyalkylene glycol mono (meth) acrylate (B-2) as part of the radical polymerizable organic compound (B);
The resin composition for optical three-dimensional modeling characterized by the above-mentioned.

And this invention,
(2) Based on the total mass of the cationically polymerizable organic compound (A), the compound (A-1) having 3 or more glycidyl etherified phenol groups in a proportion of 5 to 50% by mass and a polyalkylene glycol diglycidyl ether ( A-2) is contained in a proportion of 0.5 to 20% by mass, and polyalkylene glycol di (meth) acrylate (B-1) is contained in an amount of 5 to 70 based on the total mass of the radical polymerizable organic compound (B). It is a resin composition for optical three-dimensional model | molding of said (1) which contains the ratio of the mass% and the polyalkylene glycol mono (meth) acrylate (B-2) in the ratio of 1-35 mass%.

The present invention also provides:
(3) As a part of the cationically polymerizable organic compound (A), the following general formula (A-3);

（式中、Ｒ¹は、水素添加ビスフェノールＡ残基、水素添加ビスフェノールＥ残基、水素添加ビスフェノールＦ残基、水素添加ビスフェノールＡＤ残基、水素添加ビスフェノールＺ残基、シクロヘキサンジメタノール残基またはトリシクロデカンジメタノール残基を示す。）
で表される脂環族ジグリシジルエーテル化合物（Ａ−３）、脂環式エポキシ化合物（Ａ−４）およびオキセタン化合物（Ａ−５）から選ばれる化合物の少なくとも１種を更に含有する前記（１）または（２）の光学的立体造形用樹脂組成物；
（４） ラジカル重合性有機化合物（Ｂ）の一部として、（メタ）アクリロイルオキシ基を３個以上有するポリアクリル化合物（Ｂ−３）を更に含有する前記（１）〜（３）のいずれかの光学的立体造形用樹脂組成物；および、
（５） 光学的立体造形用樹脂組成物の全質量に基づいて、カチオン重合性有機化合物（Ａ）を３０〜８５質量％、ラジカル重合性有機化合物（Ｂ）を１０〜５０質量％、カチオン重合開始剤（Ｃ）を０．１〜１０質量％およびラジカル重合開始剤（Ｄ）を０．１〜１０質量％の割合で含有する前記した（１）〜（４）のいずれかの光学的立体造形用樹脂組成物；
である。

Wherein R ¹ is hydrogenated bisphenol A residue, hydrogenated bisphenol E residue, hydrogenated bisphenol F residue, hydrogenated bisphenol AD residue, hydrogenated bisphenol Z residue, cyclohexanedimethanol residue or tri Cyclodecanedimethanol residue is shown.)
(1) further containing at least one compound selected from the group consisting of an alicyclic diglycidyl ether compound (A-3), an alicyclic epoxy compound (A-4) and an oxetane compound (A-5) represented by the formula (1). ) Or (2) a resin composition for optical three-dimensional modeling;
(4) Any of the above (1) to (3), which further contains a polyacryl compound (B-3) having three or more (meth) acryloyloxy groups as part of the radical polymerizable organic compound (B) A resin composition for optical three-dimensional modeling; and
(5) 30 to 85% by mass of the cationic polymerizable organic compound (A), 10 to 50% by mass of the radical polymerizable organic compound (B) based on the total mass of the resin composition for optical three-dimensional modeling, and cationic polymerization The optical solid according to any one of the above (1) to (4), which contains 0.1 to 10% by mass of the initiator (C) and 0.1 to 10% by mass of the radical polymerization initiator (D). Resin composition for modeling;
It is.

Furthermore, the present invention provides
(6) A method for producing a three-dimensional model by performing optical three-dimensional modeling using the resin composition for optical three-dimensional modeling according to any one of (1) to (5); and
(7) Optical three-dimensional modeling is performed using the resin composition for optical three-dimensional modeling of any one of (1) to (5) to manufacture a three-dimensional model, and the three-dimensional model obtained thereby is obtained at 50 ° C. A method for producing a three-dimensional object with improved heat resistance, characterized by heat treatment at the above temperature;
It is.

In the resin composition for optical three-dimensional modeling containing the cationic polymerizable organic compound (A), the radical polymerizable organic compound (B), the cationic polymerization initiator (C) and the radical polymerization initiator (D),
As part of the cationically polymerizable organic compound (A), it contains a compound (A-1) having 3 or more glycidyl etherified phenol groups and a polyalkylene glycol diglycidyl ether (A-2), and a radical polymerizable organic The resin composition for optical three-dimensional modeling of the present invention containing polyalkylene glycol di (meth) acrylate (B-1) and polyalkylene glycol mono (meth) acrylate (B-2) as a part of compound (B). Is equipped with the basic physical properties necessary for a resin composition for optical three-dimensional modeling, such as high curing sensitivity by active energy rays, low viscosity, excellent handleability, and high resolution during optical three-dimensional modeling, By performing optical three-dimensional modeling (hereinafter sometimes referred to as “optical modeling”) using the resin composition for optical three-dimensional modeling A three-dimensional structure that has a high heat distortion temperature, excellent heat resistance, low yellowness, high light transmittance, excellent color tone and transparency, and excellent mechanical properties such as impact resistance and breaking strength. Can be obtained.
In addition, the heat distortion temperature is further increased by heat-treating the three-dimensional object obtained by optical modeling using the resin composition for optical three-dimensional modeling of the present invention at a temperature of 50 ° C. or higher. A further improved three-dimensional model can be obtained.
Therefore, the resin composition for optical three-dimensional modeling of the present invention has high heat resistance, high transparency, no yellow coloring, excellent transparency and color tone, and excellent impact resistance, toughness, durability, and strength. 3D modeling objects that are required, for example, models for verifying the functionality and appearance design of various industrial products during design, resin molds for manufacturing molds, base models for manufacturing molds, automobiles And motorcycle lenses, restoration of art, imitation and modern art, art and craft fields such as glass-based architectural design presentation models, precision parts, electrical and electronic parts, furniture, building structures, automotive parts, various Effective for various uses such as containers, castings, railroad models, construction machinery, industrial robots, airplane control parts, especially for automotive parts It can be used.

The present invention is described in detail below.
The resin composition for optical three-dimensional model | molding of this invention is a resin composition used in order to manufacture a three-dimensional model | molded object by irradiating active energy rays, such as light, and performing optical modeling.
The resin composition for optical three-dimensional modeling of the present invention comprises a cationic polymerizable organic compound (A) and a radical polymerizable organic compound (B) as an active energy ray polymerizable compound that is polymerized by irradiation with active energy rays such as light. contains.
As used herein, the term “active energy rays” refers to energy rays that can cure the resin composition for optical three-dimensional modeling, such as ultraviolet rays, electron beams, X-rays, radiation, and high frequencies.

The cationically polymerizable organic compound (A) used in the present invention is a compound that causes a polymerization reaction and / or a crosslinking reaction when irradiated with an active energy ray such as light in the presence of the cationic polymerization initiator (C).
In the present invention, as a part of the cationically polymerizable organic compound (A), a compound (A-1) having three or more glycidyl etherified phenol groups in one molecule [hereinafter simply referred to as “compound (A-1)”. Contains].
Compound (A-1) is represented by the following formula (A-1a);

で表されるグリシジルエーテル化フェノール基を、１分子中に３個以上有する化合物である。
本発明の光学的立体造形用樹脂組成物は、カチオン重合性有機化合物（Ａ）の一部として、化合物（Ａ−１）を含有することによって、光造形して得られる立体造形物の熱変形温度が高くて耐熱性に優れ、しかも光造形して得られる立体造形物を５０℃以上の温度で熱処理することによって熱変形温度が一層高くなって、耐熱性の一層向上した立体造形物を得ることができる。

Is a compound having 3 or more glycidyl etherified phenol groups in one molecule.
The resin composition for optical three-dimensional model | molding of this invention contains the compound (A-1) as a part of cationically polymerizable organic compound (A), and is thermally deformed of the three-dimensional model | molding thing obtained by optical modeling. The heat distortion temperature is further increased by heat-treating a three-dimensional structure obtained by optical modeling at a temperature of 50 ° C. or higher to obtain a three-dimensional structure having further improved heat resistance. be able to.

As the compound (A-1), any compound can be used as long as the viscosity of the resin composition for optical three-dimensional modeling can be maintained at a viscosity suitable for optical modeling even when the compound (A-1) is contained. .
Specific examples of the compound (A-1) that can be used in the present invention include polyglycidyl ethers of phenolic resins such as novolak resins and resol resins, tetraglycidyl ethers of tetraphenolethane, triglycidyl ethers of triphenolmethane, VG3101L represented by the chemical formula, that is, 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [1,1-bis [4-([2,3-epoxypropoxy] phenyl]] And ethyl] phenyl] propane.

  The resin composition for optical three-dimensional model | molding of this invention can contain the 1 type (s) or 2 or more types of the compounds quoted above as a compound (A-1). Among them, in the present invention, VG3101L is preferably used as the compound (A-1) from the viewpoints of obtaining a three-dimensional structure that is easily available, has little coloring, and is excellent in heat resistance and mechanical properties.

The content ratio of the compound (A-1) is preferably 5 to 50% by mass based on the total mass of the cationically polymerizable organic compound (A) contained in the optical three-dimensional resin composition. More preferably, it is 45 mass%, and it is still more preferable that it is 20-40 mass%.
If the content ratio of the compound (A-1) is too small, the thermal deformation temperature of the three-dimensional modeled object obtained by optical modeling becomes low, and heat is generated even if the three-dimensional modeled object is heat-treated at a temperature of 50 ° C. or higher after the optical modeling. It becomes difficult to increase the deformation temperature. On the other hand, when the content ratio of the compound (A-1) is too large, it takes time until the viscosity of the resin composition for optical three-dimensional modeling becomes high and the liquid level is stabilized, the optical modeling time becomes long, and bubbles are generated. This makes it easy to mix bubbles into the three-dimensional model, and the three-dimensional model obtained by optical modeling has low toughness and becomes brittle, and the transparency tends to decrease.

The resin composition for optical three-dimensional model | molding of this invention contains polyalkylene glycol diglycidyl ether (A-2) further as a part of cationically polymerizable organic compound (A).
The resin composition for optical three-dimensional model | molding of this invention contains the polyalkylene glycol diglycidyl ether (A-2) as a part of cationically polymerizable organic compound (A), and is three-dimensional model | molded obtained by optical modeling. The impact strength of the object is improved and the yellowness is low.
Specific examples of the polyalkylene glycol diglycidyl ether (A-2) include polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether, polyoxyethylene polyoxypropylene glycol diglycidyl ether, branched Polytetramethylene glycol diglycidyl ether can be used, and one or more of these can be used.
As polyalkylene glycol diglycidyl ether (A-2), those having an average molecular weight in the range of 200 to 4000, more preferably in the range of 300 to 2000, and particularly in the range of 400 to 1000, are easy to obtain, have a low melting point and are easy to handle. It is preferably used because it is excellent and the transparency of the three-dimensional modeled object obtained by optical modeling is increased.
Among them, in the present invention, as polyalkylene glycol diglycidyl ether (A-2), polytetramethylene glycol diglycidyl ether, especially polytetramethylene glycol diglycidyl ether having an average molecular weight in the range of 500 to 800 or branched. Polytetramethylene glycol diglycidyl ether is preferably used because it has a low viscosity and excellent handleability, and has a high impact strength, excellent sliding property and high transparency.

The content ratio of the polyalkylene glycol diglycidyl ether (A-2) is 0.5 to 20% by mass based on the total mass of the cationically polymerizable organic compound (A) contained in the optical three-dimensional resin composition. It is preferably 1 to 15% by mass, more preferably 3 to 10% by mass.
When the content ratio of the polyalkylene glycol diglycidyl ether (A-2) is too small, the impact resistance of the three-dimensional structure obtained by optical modeling is lowered, the yellowness is increased, and the slidability is easily lowered. . On the other hand, when the content ratio of polyalkylene glycol diglycidyl ether (A-2) is too large, the three-dimensional structure obtained by optical modeling is soft and has a low heat distortion temperature, poor transparency, and poor moisture resistance. The dimensions are likely to change.

The resin composition for optical three-dimensional model | molding of this invention is a compound (A-1) which has three or more glycidyl etherification phenol groups in a molecule | numerator as a cationically polymerizable organic compound (A), and polyalkylene glycol diglycidyl ether ( A-2) and other cationically polymerizable organic compounds can be contained as required.
The other cationically polymerizable organic compound is a compound other than the compound (A-1) and the polyalkylene glycol diglycidyl ether (A-2), and has an activity such as light in the presence of the cationic polymerization initiator (C). Any compound may be included as long as it is an organic compound that causes a cationic polymerization reaction and / or a cationic crosslinking reaction when irradiated with energy rays.
Examples of other cationically polymerizable organic compounds that can be optionally contained in the present invention include epoxy compounds other than the compound (A-1) and polyalkylene glycol diglycidyl ether (A-2), oxetane compounds and other A cyclic ether compound, a cyclic acetal compound, a cyclic lactone compound, a spiro orthoester compound, a vinyl ether compound, and the like can be given, and one or more of these cationically polymerizable organic compounds can be contained.
Among these, the preferable thing among the other cationically polymerizable organic compounds which the resin composition for optical three-dimensional model | molding of this invention can contain as needed is a compound (A-1) and polyalkylene glycol diglycidyl ether ( Epoxy compounds and / or oxetane compounds other than A-2).

  As other epoxy compounds [epoxy compounds other than compound (A-1) and polyalkylene glycol diglycidyl ether (A-2)] that may be contained as necessary, other than polyalkylene glycol diglycidyl ether (A-2) An aliphatic epoxy compound, an alicyclic epoxy compound having a glycidyl group, an alicyclic epoxy compound, an aromatic epoxy compound other than the compound (A-1), and the like.

  Examples of the aliphatic epoxy compound other than polyalkylene glycol diglycidyl ether (A-2) that can be contained as needed include aliphatic polyhydric alcohols other than polyalkylene glycol diglycidyl ether (A-2) or the like Polyglycidyl ethers of alkylene oxide adducts, polyglycidyl esters of aliphatic long-chain polybasic acids, homopolymers synthesized by vinyl polymerization of glycidyl acrylate or glycidyl methacrylate, vinyl polymerization of glycidyl acrylate and / or glycidyl methacrylate with other vinyl monomers And the like.

Specific examples include butyl glycidyl ether, 2-ethylhexyl glycidyl ether, glycidyl ether of higher alcohol, diglycidyl ether of alkylene diol (for example, diglycidyl ether of 1,4-butanediol, diglycidyl of 1,6-hexanediol Ether, neopentyl glycol diglycidyl ether), glycerin triglycidyl ether, trimethylolpropane diglycidyl ether, trimethylolpropane triglycidyl ether, sorbitol tetraglycidyl ether, dipentaerythritol hexaglycidyl ether Mention may be made of glycidyl ethers of monohydric alcohols.
Furthermore, polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as trimethylolpropane and glycerin, diglycidyl esters of aliphatic long-chain dibasic acids, etc. Can be mentioned.
Furthermore, monoglycidyl ethers of higher aliphatic alcohols, glycidyl esters of higher fatty acids, epoxidized soybean oil, butyl epoxy stearate, epoxidized polybutadiene, glycidylated polybutadiene and the like can be mentioned.
In addition, epoxy alkanes such as 1,2-epoxydecane, 1,2-epoxydodecane, 1,2-epoxytetradecane, 1,2-epoxycetane, 1,2-epoxyoctadecane, and 1,2-epoxyicosane are listed. be able to.

  Examples of the alicyclic epoxy compound having a glycidyl group that can be contained as required include, for example, monoglycidyl ethers of cycloalkanols such as cyclohexanol and cyclopentanol, and polyoxyalkanols obtained by adding alkylene oxide to cycloalkanols. Monoglycidyl ether of ether alcohol, cyclohexanedimethanol diglycidyl ether, the following general formula (A-3);

（式中、Ｒ¹は、水素添加ビスフェノールＡ残基、水素添加ビスフェノールＥ残基、水素添加ビスフェノールＦ残基、水素添加ビスフェノールＡＤ残基、水素添加ビスフェノールＺ残基、シクロヘキサンジメタノール残基またはトリシクロデカンジメタノール残基を示す。）
で表される脂環族ジグリシジルエーテル化合物（Ａ−３）などを挙げることができる。

Wherein R ¹ is hydrogenated bisphenol A residue, hydrogenated bisphenol E residue, hydrogenated bisphenol F residue, hydrogenated bisphenol AD residue, hydrogenated bisphenol Z residue, cyclohexanedimethanol residue or tri Cyclodecanedimethanol residue is shown.)
The alicyclic diglycidyl ether compound (A-3) etc. which are represented by these can be mentioned.

  Specific examples of the alicyclic diglycidyl ether compound (A-3) include hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol AD diglycidyl ether, and hydrogenated bisphenol Z diglycidyl. Ether, cyclohexane dimethanol diglycidyl ether, tricyclodecane dimethanol diglycidyl ether), and if necessary, one or more of these can be contained.

  The alicyclic epoxy compound [hereinafter referred to as “alicyclic epoxy compound (A-4)”] which can be contained as necessary is unsaturated in an aliphatic ring such as a cyclohexene ring-containing compound or a cyclopentene ring-containing compound. A compound obtained by epoxidizing the unsaturated double bond in a cycloalkene compound having a double bond with an appropriate oxidizing agent such as hydrogen peroxide or peracid, and having a cyclohexene oxide structure, a cyclopentene oxide structure or the like. It is a compound having an alkene oxide structure.

Specific examples of the alicyclic epoxy compound (A-4) that can be contained as needed include 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 3,4-epoxy-1- Methylcyclohexyl-3,4-epoxy-1-methylcyclohexanecarboxylate, 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-3-methyl Cyclohexylmethyl-3,4-epoxy-3-methylcyclohexanecarboxylate, 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl) -5,5-spiro-3,4-epoxy) Rhohexane-metadioxane, bis (3,4-epoxycyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexylcarboxylate, dicyclopentadiene diepoxide, ethylenebis (3,4-epoxycyclohexanecarboxylate), epoxy Examples thereof include dioctyl hexahydrophthalate and di-2-ethylhexyl epoxyhexahydrophthalate.
Further, ε-caprolactone-modified 3 ′, 4′-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, 1,2-bis (hydroxymethyl) -1-butanol 1,2 sold by Daicel Chemical Industries Mention may also be made of epoxy-4- (2-oxiranyl) cyclohexane adducts.
Further, bis (3,4-epoxycyclohexyl) methane, 2,2-bis (3,4-epoxycyclohexyl) propane, 1,1-bis (3,4-epoxycyclohexyl) ethane, alpha pinene oxide, camphorene aldehyde , Limonene monooxide, limonene dioxide, 4-vinylcyclohexene monooxide, 4-vinylcyclohexene dioxide, and the like.
The resin composition for optical three-dimensional model | molding of this invention can contain these 1 type (s) or 2 or more types as needed.

Examples of the aromatic epoxy compound other than the compound (A-1) that can be contained as needed include polyglycidyl ethers and polyglycidyl esters of polyhydric phenols or alkylene oxide adducts thereof. Examples include bisphenol A, bisphenol E, bisphenol F, bisphenol AD, bisphenol Z, or glycidyl ether, phenyl glycidyl ether, tert-butylphenyl glycidyl ether of a compound obtained by further adding an alkylene oxide such as ethylene oxide or propylene oxide, Resorcinol diglycidyl ether, tetraglycidyl ether of tetraphenolethane, triglycidyl ether of triphenolmethane, phenols or naphthols Glycidylated products of condensates with aldehydes (eg phenol resins and novolak resins), glycidylated products of phenols and isopropenylacetophenone condensates, noglycidated products of phenols and dicyclopentadiene, diglycidyl terephthalate Examples include esters, diglycidyl esters of isophthalic acid, and diglycidyl esters of o-phthalic acid.
Furthermore, the diglycidyl ether of biphenol, the diglycidyl ether of tetramethylbiphenol, etc. can be mentioned.
The resin composition for optical three-dimensional model | molding of this invention can contain these 1 type (s) or 2 or more types as needed.

Moreover, as an oxetane compound [hereinafter referred to as “oxetane compound (A-5)]” that the resin composition for optical three-dimensional modeling of the present invention may contain as necessary, a monooxetane having one oxetane group in the molecule. Examples thereof include compound (A-5a) and polyoxetane compound (A-5b) having 2, 3, or 4 or more oxetane groups in the molecule.
As the monooxetane compound (A-5a), any compound having one oxetane group in one molecule can be used, and in particular, one oxetane group and one alcoholic hydroxyl group in one molecule. The monooxetane monoalcohol compound having is preferably used.
Among such monooxetane monoalcohol compounds, the monooxetane monoalcohol compound (A-5a ₁ ) represented by the following general formula (A-5a ₁ ) and the following general formula (A-5a ₂ ) At least one of the represented monooxetane monoalcohol compounds (A-5a ₂ ) is more preferably used as a monooxetane compound from the viewpoints of availability, high reactivity, and low viscosity.

（式中、Ｒ²およびＲ³は炭素数１〜５のアルキル基、Ｒ⁴はエーテル結合を有していてもよい炭素数２〜１０のアルキレン基を示す。）

(Wherein R ² and R ³ represent an alkyl group having 1 to 5 carbon atoms, and R ⁴ represents an alkylene group having 2 to 10 carbon atoms which may have an ether bond.)

In the above general formula (A-5a ₁ ), examples of R ² include methyl, ethyl, propyl, butyl, and pentyl.
Specific examples of monooxetane alcohol (A-5a ₁ ) include 3-hydroxymethyl-3-methyloxetane, 3-hydroxymethyl-3-ethyloxetane, 3-hydroxymethyl-3-propyloxetane, 3-hydroxymethyl- 3-normal butyl oxetane, 3-hydroxymethyl-3-propyl oxetane, etc. can be mentioned, These 1 type (s) or 2 or more types can be used. Among these, 3-hydroxymethyl-3-methyloxetane and 3-hydroxymethyl-3-ethyloxetane are more preferably used from the viewpoints of easy availability and reactivity.

In the above general formula (A-5a ₂ ), examples of R ³ include methyl, ethyl, propyl, butyl, and pentyl.
In the above general formula (A-5a ₂ ), R ⁴ may be either a chain alkylene group or a branched alkylene group as long as it is an alkylene group having 2 to 10 carbon atoms, or an alkylene group. A C2-C10 chain or branched alkylene group having an ether bond (ether oxygen atom) in the middle of the (alkylene chain) may be used. Specific examples of R ⁴ include ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, 3-oxypentylene group and the like. Among them, R ⁶ is preferably a trimethylene group, a tetramethylene group, a pentamethylene group or a heptamethylene group from the viewpoints of easiness of synthesis and easy handling because the compound is liquid at room temperature.

In addition, as the polyoxetane compound (A-5b), any of a compound having two oxetane groups, a compound having three oxetane groups, and a compound having four or four oxetane groups can be used. A dioxetane compound having two of them is preferably used, and among them, the following general formula (A-5b ₀ );

（式中、２個のＲ⁵は互いに同じかまたは異なる炭素数１〜５のアルキル基、Ｒ⁶は芳香環を有しているかまたは有していない２価の有機基、ｓは０または１を示す。）
で表されるジオキセタン化合物（Ａ−５ｂ₀）が、入手性、反応性、低吸湿性、硬化物の力学的特性などの点から好ましく用いられる。
上記の一般式（Ａ−５ｂ₀）において、Ｒ⁵の例としては、メチル、エチル、プロピル、ブチル、ペンチルを挙げることができる。また、Ｒ⁶の例としては、炭素数１〜１２の直鎖状または分岐状のアルキレン基（例えばエチレン基、プロピレン基、ブチレン基、ネオペンチレン基、ｎ−ペンタメチレン基、ｎ−ヘキサメチレン基など）、式：−ＣＨ₂−Ｐｈ−ＣＨ₂−または−ＣＨ₂−Ｐｈ−Ｐｈ−ＣＨ₂−で表される２価の基、水素添加ビスフェノールＡ残基、水素添加ビスフェノールＦ残基、水素添加ビスフェノールＡＤ残基、水素添加ビスフェノールＺ残基、シクロヘキサンジメタノール残基、トリシクロデカンジメタノール残基、テレフタル酸残基、イソフタル酸残基、ｏ−フタル酸残基などを挙げることができる。

(In the formula, two R ⁵ are the same or different alkyl groups having 1 to 5 carbon atoms, R ⁶ is a divalent organic group having or not having an aromatic ring, and s is 0 or 1. Is shown.)
The dioxetane compound (A-5b ₀ ) represented by the formula is preferably used in terms of availability, reactivity, low hygroscopicity, mechanical properties of the cured product, and the like.
In the above general formula (A-5b ₀ ), examples of R ⁵ include methyl, ethyl, propyl, butyl, and pentyl. Examples of R ⁶ include linear or branched alkylene groups having 1 to 12 carbon atoms (for example, ethylene group, propylene group, butylene group, neopentylene group, n-pentamethylene group, n-hexamethylene group, etc. ), A divalent group represented by the formula: —CH ₂ —Ph—CH ₂ — or —CH ₂ —Ph—Ph—CH ₂ —, hydrogenated bisphenol A residue, hydrogenated bisphenol F residue, hydrogenated Examples thereof include bisphenol AD residue, hydrogenated bisphenol Z residue, cyclohexanedimethanol residue, tricyclodecane dimethanol residue, terephthalic acid residue, isophthalic acid residue, o-phthalic acid residue and the like.

Specific examples of the dioxetane compound (A-5b ₀ ) include a dioxetane compound represented by the following formula (A-5b ₁ ) or formula (A-5b ₂ ).

（式中、２個のＲ⁷は互いに同じかまたは異なる炭素数１〜５のアルキル基、Ｒ⁸は芳香環を有しているかまたは有していない２価の有機基を示す。）

(In the formula, two R ^{7 s} are the same or different from each other, and a C 1-5 alkyl group, and R ⁸ is a divalent organic group having or not having an aromatic ring.)

Specific examples of the dioxetane compound represented by the above formula (A-5b ₁ ) include bis (3-methyl-3-oxetanylmethyl) ether, bis (3-ethyl-3-oxetanylmethyl) ether, bis (3 -Propyl-3-oxetanylmethyl) ether, bis (3-butyl-3-oxetanylmethyl) ether, and the like.
Specific examples of the dioxetane compounds represented by the above formula (A-5b _{2), 2} pieces of R ⁷ are both methyl in the above formula (A-5b _2), ethyl, propyl, butyl or pentyl group R ⁸ is ethylene group, propylene group, butylene group, neopentylene group, n-pentamethylene group, n-hexamethylene group, etc.), formula: —CH ₂ —Ph—CH ₂ — or —CH ₂ —Ph—Ph A divalent group represented by —CH ₂ —, hydrogenated bisphenol A residue, hydrogenated bisphenol F residue, hydrogenated bisphenol AD residue, hydrogenated bisphenol Z residue, cyclohexanedimethanol residue, tricyclode The dioxetane compound which is a candimethanol residue, a terephthalic acid residue, an isophthalic acid residue, and an o-phthalic acid residue can be mentioned.
Among them, as the polyoxetane compound (A-5b ₀ ), in the above formula (A-5b ₁ ), bis (3-methyl-3-oxetanylmethyl) in which two R ^{7 s} are both methyl groups or ethyl groups. ) Ether and / or bis (3-ethyl-3-oxetanylmethyl) ether are preferably used from the viewpoints of availability, low hygroscopicity, mechanical properties of the cured product, and the like. -Oxetanylmethyl) ether is more preferably used.

The resin composition for optical three-dimensional model | molding of this invention is an alicyclic diglycidyl ether compound with a compound (A-1) and a polyalkylene glycol diglycidyl ether (A-2) as a cationically polymerizable organic compound (A). It preferably contains at least one compound selected from (A-3), an alicyclic epoxy compound (A-4) and an oxetane compound (A-5), and more preferably contains two or more. More preferably, it contains all of the alicyclic diglycidyl ether compound (A-3), the alicyclic epoxy compound (A-4) and the oxetane compound (A-5).
When the alicyclic diglycidyl ether compound (A-3) is contained, the photocuring sensitivity of the resin composition for optical three-dimensional modeling is improved, and the three-dimensional model is produced with high productivity in a reduced active energy ray irradiation time. It becomes possible to manufacture, absorption of moisture and moisture of the three-dimensional modeled object obtained by optical modeling is reduced, impact strength is improved, and transparency is increased.
When the alicyclic epoxy compound (A-4) is contained, the photocuring speed of the resin composition for optical three-dimensional modeling is improved, and a three-dimensional model can be obtained in a short time for reaction. As a result, the heat deformation temperature of the three-dimensional structure obtained is increased, the hardness is increased, and the rigidity is improved.
When the oxetane compound (A-5) is contained, the viscosity of the photocurable resin composition is lowered, the handleability and the photoformability are improved, and the photocuring speed of the optical three-dimensional resin composition is improved. A three-dimensional model is obtained in a short time, and the impact strength, thermal deformation temperature, toughness, etc. of the three-dimensional model obtained by optical modeling are improved.

The resin composition for optical three-dimensional modeling of the present invention is an oxetane compound (A- As 5), it is preferable to contain the monooxetane compound (A-5a) alone or to contain both the monooxetane compound (A-5a) and the polyoxetane compound (A-5b).
In the case where the monooxetane compound (A-5a) and the polyoxetane compound (A-5b) are contained as the oxetane compound (A-5), both are converted into the monooxetane compound (A-5a): the polyoxetane compound (A-5b). ) = 95: 5 to 5:95 It is preferable to contain by mass ratio, It is more preferable to contain by mass ratio of 90:10 to 10:90, It contains by mass ratio of 25:75 to 75:25 More preferably.

At least a compound selected from the alicyclic diglycidyl ether compound (A-3), the alicyclic epoxy compound (A-4), and the oxetane compound (A-5) in the resin composition for optical three-dimensional modeling of the present invention. When one is contained, the content ratio of the alicyclic diglycidyl ether compound (A-3) is 0 to 0 based on the total mass of the cationically polymerizable organic compound (A) contained in the photocurable resin composition. 50% by mass, especially 5-30% by mass, content of alicyclic epoxy compound (A-4) is 0-50% by mass, especially 5-30% by mass, content of oxetane compound (A-5) is 0 It is preferable that it is -60 mass%, especially 5-40 mass%.
Moreover, the total content rate of an alicyclic diglycidyl ether compound (A-3), an alicyclic epoxy compound (A-4), and an oxetane compound (A-5) is contained in the resin composition for optical three-dimensional modeling. Based on the total mass of the cationically polymerizable organic compound (A), it is preferably 0 to 70% by mass, more preferably 20 to 65% by mass, and still more preferably 30 to 60% by mass. When the total content of the three components exceeds 70% by mass based on the total mass of the cationic polymerizable organic compound (A), the content of the essential component (A-1) is relatively reduced, and light The heat distortion temperature of the three-dimensional object obtained by modeling decreases, the heat resistance decreases, the moisture resistance also decreases, and even if the three-dimensional object obtained by optical modeling is heat-treated at 50 ° C. or higher, the heat distortion temperature No further improvement is obtained, and the heat treatment increases the yellowness of the three-dimensional structure and decreases the transmittance and color tone.

The radically polymerizable organic compound (B) used in the present invention is a compound that undergoes a polymerization reaction and / or a crosslinking reaction when irradiated with an active energy ray such as light in the presence of the radical polymerization initiator (D).
The resin composition for optical three-dimensional modeling of the present invention includes a polyalkylene glycol di (meth) acrylate (B-1) and a polyalkylene glycol mono (meth) acrylate (B) as part of the radical polymerizable organic compound (B). -2).

Examples of the polyalkylene glycol di (meth) acrylate (B-1) used in the present invention include polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, polypropylene glycol diacrylate, polypropylene glycol dimethacrylate, and poly (oxyethylene / oxypropylene random copolymer). Diol) diacrylate of diol, poly (oxyethylene / oxypropylene random copolymer) diol dimethacrylate, polyoxyethylene polymer block / polyoxypropylene polymer block-bonded block copolymer having hydroxyl groups at both ends (Block copolymer diol) diacrylate or dimethacrylate, polytetramethylene glycol diacrylate, polytetramethylene glycol dimethyl ester Random copolymer diol diacrylate or dimethacrylate, polyoxyethylene polymer block / polytetramethylene glycol polymer block in which acrylate, ethylene oxide unit and tetramethylene oxide unit are randomly bonded and have hydroxyl groups at both ends Examples thereof include a diacrylate or dimethacrylate of a block copolymer having a hydroxyl group at both ends (block copolymer diol).
Among them, in the present invention, the polyalkylene glycol di (meth) acrylate (B-1) is easily available, is liquid at room temperature, has excellent handleability, and a molded product obtained from an optical three-dimensional model is transparent. Of polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, polypropylene glycol diacrylate, polypropylene glycol dimethacrylate, polytetramethylene glycol diacrylate, polytetramethylene glycol dimethacrylate One or more are preferably used, and polyethylene glycol diacrylate, polypropylene glycol diacrylate and polytetramethylene glycol diacrylate are more preferably used. . In particular, when polytetramethylene glycol diacrylate is used as the polyalkylene glycol di (meth) acrylate (B-1), in addition to the above-described properties, the impact resistance of the three-dimensional structure obtained by optical modeling is more excellent. In addition, the absorption of moisture and moisture is smaller and the dimensional stability is more excellent.

From the viewpoints of various properties such as solubility in optical three-dimensional modeling resin composition, miscibility, impact strength, toughness, and durability of the three-dimensional modeled product obtained by photocuring. The average molecular weight of the alkylene glycol di (meth) acrylate (B-1) is preferably 300 to 2000, more preferably 500 to 1500, and still more preferably 600 to 1200.
If the molecular weight of the polyalkylene glycol di (meth) acrylate (B-1) is too small, the impact strength of the three-dimensional structure obtained by stereolithography is reduced, resulting in low toughness and flexibility, while the polyalkylene glycol di ( When the molecular weight of the (meth) acrylate (B-1) is too large, the solubility in the resin composition for optical three-dimensional modeling is reduced, or the optical system in which polyalkylene glycol di (meth) acrylate (B-1) is added. The viscosity of the three-dimensional modeled resin composition is increased, the light transmittance of the three-dimensional modeled product obtained by optical modeling is lowered, and in some cases, it tends to be opaque.

Although not limited, Among the polyalkylene glycol di (meth) acrylates (B-1) used in the present invention, as specific examples of polyethylene glycol di (meth) acrylates,
* “Blemmer ADE-200” manufactured by NOF Corporation, “A-200” manufactured by Shin-Nakamura Chemical Co., Ltd., “Light Acrylate 4EG-A” manufactured by Kyoeisha Chemical Co., Ltd. Polyethylene glycol diacrylate having an average molecular weight ≈ 300);
* “Blemmer ADE-400” manufactured by NOF Corporation, “N-Nakamura Chemical Co., Ltd.“ A-400 ”,“ Light Acrylate 9EG-A ”manufactured by Kyoeisha Chemical Co., Ltd.,“ FA-240A ”manufactured by Hitachi Chemical Co., Ltd. And polyethylene glycol diacrylate having a number of bonds of ethylene oxide units≈9 and an average molecular weight≈500);
* Shin-Nakamura Chemical Co., Ltd. “A-600” (polyethylene glycol diacrylate having an ethylene oxide unit bond number≈14 and an average molecular weight≈750);
* Shin-Nakamura Chemical Co., Ltd. “A-1000” (polyethylene glycol diacrylate having an ethylene oxide unit bond number≈23 and an average molecular weight≈1100);
* “Blemmer DPE-200” manufactured by NOF Corporation, “4G” manufactured by Shin-Nakamura Chemical Co., Ltd., “FA-220M” manufactured by Hitachi Chemical Co., Ltd. Polyethylene glycol dimethacrylate);
* “Blemmer DPE-400” manufactured by NOF Corporation, “9G” manufactured by Shin-Nakamura Chemical Co., Ltd. (both polyethylene glycol dimethacrylates having an ethylene oxide unit bond number of about 9 and an average molecular weight of about 530 to 540);
* “Blemmer DPE-600” (manufactured by NOF Corporation) (polyethylene glycol dimethacrylate having a number of bonds of ethylene oxide units≈13 and an average molecular weight≈690);
* Shin-Nakamura Chemical Co., Ltd. “14G” (ethylene glycol dimethacrylate having an ethylene oxide unit number of bonds ≈ 14 and an average molecular weight ≈ 740);
* “23G” manufactured by Shin-Nakamura Chemical Co., Ltd. (polyethylene glycol dimethacrylate having an ethylene oxide unit bond number≈23 and an average molecular weight≈1140);
And so on.

As specific examples of polypropylene glycol di (meth) acrylate that can be used in the present invention,
* “APG-200” manufactured by Shin-Nakamura Chemical Co., Ltd. (polypropylene glycol diacrylate having a number of bonds of propylene oxide units≈3 and an average molecular weight≈300);
* "Blemmer ADP-200" (manufactured by NOF Corporation) (polypropylene glycol dimethacrylate having a number of bonds of propylene oxide units of about 4 and an average molecular weight of about 360);
* “APG-400” manufactured by Shin-Nakamura Chemical Co., Ltd., “FA-P240A” manufactured by Hitachi Chemical Co., Ltd. (both polypropylene glycol diacrylates having a bond number of propylene oxide units ≈ 7 and an average molecular weight ≈ 530-540);
* “Blemmer ADP-400” (manufactured by NOF Corporation) (polypropylene glycol dimethacrylate having a propylene oxide unit bond number≈9 and an average molecular weight≈650);
* “FA-P270A” manufactured by Hitachi Chemical Co., Ltd. (polypropylene glycol diacrylate having a number of bonds of propylene oxide units≈12 and an average molecular weight≈820);
* “APG-700” manufactured by Shin-Nakamura Chemical Co., Ltd. (polypropylene glycol diacrylate having a number of bonds of propylene oxide units≈12 and an average molecular weight≈810);
* “9PG” manufactured by Shin-Nakamura Chemical Co., Ltd. (polypropylene glycol dimethacrylate having a number of bonds of propylene oxide units of about 7 and an average molecular weight of about 540);
* “Blemmer PDP-400” manufactured by NOF Corporation (polypropylene glycol dimethacrylate having a number of bonds of propylene oxide units of about 9 and an average molecular weight of about 680);
And so on.

Specific examples of polytetramethylene glycol di (meth) acrylate that can be used in the present invention include:
* “A-PTMG-65” manufactured by Shin-Nakamura Chemical Co., Ltd. (polytetramethylene glycol diacrylate having a tetramethylene oxide unit bond number≈9 and an average molecular weight≈750);
* “FA-PTG9A” manufactured by Hitachi Chemical Co., Ltd. (polytetramethylene glycol diacrylate having a tetramethylene oxide unit bond number≈9 and an average molecular weight≈770);
* “A-PTMG-100” manufactured by Shin-Nakamura Chemical Co., Ltd. (polytetramethylene glycol diacrylate having a tetramethylene oxide unit bond number≈14 and an average molecular weight≈1130);
* “Blemmer PDT-800” manufactured by NOF Corporation (polytetramethylene glycol dimethacrylate having a bond number of tetramethylene oxide units≈11 and an average molecular weight≈920);
And so on.

  Specific examples of other polyalkylene glycol di (meth) acrylates that can be used in the present invention include “Blenmer PDET” (dimethacrylate of poly (oxyethylene / oxypropylene) block copolymer diol) manufactured by NOF Corporation, “Blenmer ADET” (diacrylate of poly (oxyethylene / oxypropylene) block copolymer diol), “Blenmer PDPT” (dimethacrylate of poly (oxypropylene / oxytetramethylene) copolymer diol), “Blenmer ADPT” (Diacrylate of poly (oxypropylene / oxytetramethylene) block copolymer diol), “Blenmer PDC” (dimethacrylate of poly (oxyethylene / oxypropylene / oxyethylene) copolymer diol), Mer ADC "(poly (oxyethylene / oxypropylene / oxyethylene) diacrylate block copolymer diol) and the like.

  Among the polyalkylene glycol di (meth) acrylates listed above, polyethylene glycol diacrylate, polypropylene glycol diacrylate, and polytetramethylene glycol diacrylate are liquid at room temperature and are easy to obtain. It is preferably used from the viewpoint that a certain point, the reactivity is high, and a three-dimensional model can be obtained quickly. Among them, when polytetramethylene glycol diacrylate is used alone, or when polytetramethylene glycol diacrylate and one or both of polyethylene glycol diacrylate and polypropylene glycol diacrylate are used in combination, the toughness of the optically shaped article is further increased. More preferred.

The content ratio of the polyalkylene glycol di (meth) acrylate (B-1) in the resin composition for optical three-dimensional modeling is based on the total mass of the radical polymerizable organic compound (B) contained in the resin composition for optical three-dimensional modeling. Based on this, it is preferably 5 to 70% by mass, more preferably 10 to 60% by mass, and still more preferably 20 to 50% by mass.
If the content ratio of the polyalkylene glycol di (meth) acrylate (B-1) is too small, the impact strength of the three-dimensional model obtained by optical modeling is reduced, and the toughness of the three-dimensional model is reduced, and the three-dimensional model is obtained. The yellowness of the light increases, and the light transmittance decreases.
On the other hand, if the content ratio of the polyalkylene glycol di (meth) acrylate (B-1) is too large, the flexibility of the three-dimensional structure obtained by optical modeling becomes excessive, and the heat resistance and rigidity of the three-dimensional structure decrease. In addition, the absorption rate of moisture and moisture is increased and the dimensional stability is lowered.

  As polyalkylene glycol mono (meth) acrylate (B-2) used in the present invention, polyethylene glycol monoacrylate, polyethylene glycol monomethacrylate, polypropylene glycol monoacrylate, polypropylene glycol monomethacrylate, poly (oxyethylene / oxypropylene random copolymer) (Polymer) Diol monoacrylate, Poly (oxyethylene / oxypropylene random copolymer) diol monomethacrylate, Polyoxyethylene polymer block / Polyoxypropylene polymer block-bonded block copolymer having hydroxyl groups at both ends (Block copolymer monool) monoacrylate or monomethacrylate, polytetramethylene glycol monoacrylate, polytetra Tylene glycol monomethacrylate, random copolymer diol monoacrylate or monomethacrylate, polyoxyethylene polymer block / polytetramethylene glycol polymer block in which ethylene oxide units and tetramethylene oxide units are randomly bonded and have hydroxyl groups at both ends A monoacrylate or monomethacrylate of a block copolymer (block copolymer monool) having hydroxyl groups at both ends to which is bonded.

  Among them, in the present invention, the polyalkylene glycol mono (meth) acrylate (B-2) is easily available, is liquid at room temperature, has excellent handleability, and a molded product obtained from an optical three-dimensional model is transparent. Of polyethylene glycol monoacrylate, polyethylene glycol monomethacrylate, polypropylene glycol monoacrylate, polypropylene glycol monomethacrylate, polytetramethylene glycol monoacrylate, polytetramethylene glycol monomethacrylate One or more are preferably used, and polyethylene glycol monoacrylate, polypropylene glycol monoacrylate and polytetramethylene glycol monoacrylate are used. Ri is preferably used. In particular, when polypropylene glycol monoacrylate is used as the polyalkylene glycol mono (meth) acrylate (B-2), in addition to the above-described properties, the photocurable resin composition has excellent photocurability, and light The impact resistance of the three-dimensional model obtained by modeling becomes more excellent.

From the viewpoints of various properties such as solubility in optical three-dimensional modeling resin composition, miscibility, impact strength, toughness, and durability of the three-dimensional modeled product obtained by photocuring. The average molecular weight of the alkylene glycol mono (meth) acrylate (B-2) is preferably 150 to 1200, more preferably 150 to 1000, and even more preferably 200 to 700.
If the molecular weight of the polyalkylene glycol mono (meth) acrylate (B-2) is too small, the impact strength of the three-dimensional modeled object obtained by stereolithography is reduced and the toughness and flexibility are lowered, while the polyalkylene glycol mono ( If the molecular weight of the (meth) acrylate (B-2) is too large, the solubility in the resin composition for optical three-dimensional modeling is reduced, or the optical system in which the polyalkylene glycol mono (meth) acrylate (B-2) is added. The viscosity of the three-dimensional modeled resin composition is increased, the photocurability is lowered, and the hardness of the three-dimensional modeled product obtained by optical modeling is likely to be soft.

Although not limited, As a specific example of the polyalkylene glycol mono (meth) acrylate (B-2) used in the present invention,
-"Blemmer AE90" manufactured by Nippon Oil & Fats Co., Ltd. (monoacrylate of polyethylene glycol having a number of bonds of ethylene oxide units ≈ 2 and an average molecular weight of about 90);
“Nippon Yushi Co., Ltd.“ Blenmer AE200 ”(ethylene oxide monoacrylate having an average molecular weight of about 200, the number of bonds of ethylene oxide units≈4.5);
“Blemmer AE400” manufactured by Nippon Oil & Fats Co., Ltd. (monoethylene acrylate of polyethylene glycol having an ethylene oxide unit bond number of about 10 and an average molecular weight of about 400);
"Nippon Yushi Co., Ltd." Blenmer PE90 "(ethylene glycol monomethacrylate having a number of bonds of ethylene oxide units ≈ 2 and an average molecular weight of about 90);
“Nippon Yushi Co., Ltd.“ Blenmer PE200 ”(ethylene glycol monomethacrylate having an ethylene oxide unit bond number of about 4.5 and an average molecular weight of about 200);
“Nippon Yushi Co., Ltd.“ Blenmer PE350 ”(ethylene glycol monomethacrylate having a number of bonds of ethylene oxide units≈8 and an average molecular weight of about 350);
"Blemmer AP150" manufactured by Nippon Oil & Fats Co., Ltd. (monoacrylate of polypropylene glycol having a number of bonds of propylene oxide units of about 3 and an average molecular weight of about 150);
・ Nippon Yushi Co., Ltd. “Blemmer AP250” (Number of bonds of propylene oxide unit ≒
4, monoacrylate of polypropylene glycol having an average molecular weight of about 250);
“Blenmer AP400” manufactured by Nippon Oil & Fats Co., Ltd. (monoacrylate of polypropylene glycol having a number of bonds of propylene oxide units≈6 and an average molecular weight of about 400);
“Nippon Yushi Co., Ltd.“ Blenmer AP550 ”(Propylene glycol monoacrylate having a number of bonds of propylene oxide units≈9 and an average molecular weight of about 550);
“Blemmer AP800” (manufactured by Nippon Oil & Fats Co., Ltd.) (polypropylene glycol monoacrylate having a number of bonds of propylene oxide units of about 13 and an average molecular weight of about 800);
-"Blenmer PP500" manufactured by Nippon Oil & Fats Co., Ltd. (monomethacrylate of polypropylene glycol having a number of bonds of propylene oxide units of about 9 and an average molecular weight of about 500);
“Blenmer PP800” manufactured by Nippon Oil & Fats Co., Ltd. (polypropylene glycol monomethacrylate having a number of bonds of propylene oxide units of about 13 and an average molecular weight of about 800);
And so on.

As further specific examples of the polyalkylene glycol mono (meth) acrylate (B-2) that can be used in the present invention,
"Blemmer 10AEP550B" manufactured by Nippon Oil & Fats Co., Ltd. (monoacrylate of polyethylene glycol polypropylene glycol having a number of bonds of ethylene oxide units ≈ 1, a number of bonds of propylene oxide units ≈ 9, and an average molecular weight of about 550);
-“Blenmer 10PEP550B” manufactured by Nippon Oil & Fats Co., Ltd. (monomethacrylate of polyethylene glycol polypropylene glycol having a number of bonds of ethylene oxide units ≈ 1, a number of bonds of propylene oxide units ≈ 9 and an average molecular weight of about 550);
“Blenmer 55PET400” manufactured by Nippon Oil & Fats Co., Ltd. (ethylene oxide tetramethylene glycol monomethacrylate having a number of bonds of ethylene oxide units≈5, a number of bonds of tetramethylene glycol units≈3, and an average molecular weight of about 400);
“Blemmer 55AET800” manufactured by Nippon Oil & Fats Co., Ltd. (monoacrylate of polyethylene glycol tetramethylene glycol having the number of bonds of ethylene oxide units≈10, the number of bonds of tetramethylene glycol units≈5, and the average molecular weight≈800);
“Blemmer 55PET800” manufactured by Nippon Oil & Fats Co., Ltd. (monomethacrylate of polyethylene glycol tetramethylene glycol having a number of bonds of ethylene oxide units≈10, a number of bonds of tetramethylene glycol units≈5, and an average molecular weight of about 800);
"Nippon Yushi Co., Ltd." Blenmer 30PPT800 "(propylene glycol tetramethylene glycol monomethacrylate having a number of bonds of propylene oxide units ≈ 4, a number of bonds of tetramethylene glycol units ≈ 8, an average molecular weight of about 800);
“Blemmer 50APT800” manufactured by Yushi Co., Ltd. (polypropylene glycol tetramethylene glycol monoacrylate having a number of bonds of propylene oxide units ≈ 7, a number of bonds of tetramethylene glycol units ≈ 5.5, and an average molecular weight of about 800);
"Nippon Yushi Co., Ltd." Blemmer 50PPT800 "(Propylene oxide unit bond number ≈ 7, Tetramethylene glycol unit bond number ≈ 5.5, Polypropylene glycol tetramethylene glycol monomethacrylate having an average molecular weight of about 800);
-“Blemmer 70PPT800” manufactured by Nippon Oil & Fats Co., Ltd. (monomethacrylate of polypropylene glycol tetramethylene glycol having a number of bonds of propylene oxide units≈10, a number of bonds of tetramethylene glycol units≈3, and an average molecular weight of about 800);
And so on.

  Among the polyalkylene glycol mono (meth) acrylates mentioned above, Blemmer AE90, Blemmer AE200, Blemmer AE400, Blemmer AP150, Blemmer AP250, Blemmer AP400, Blemmer AP550 are preferably used from the viewpoint of availability.

The content ratio of the polyalkylene glycol mono (meth) acrylate (B-2) in the resin composition for optical three-dimensional modeling is based on the total mass of the radical polymerizable organic compound (B) contained in the resin composition for optical three-dimensional modeling. Based on this, it is preferably 1 to 35% by mass, more preferably 5 to 30% by mass, and still more preferably 10 to 25% by mass.
When the content ratio of the polyalkylene glycol mono (meth) acrylate (B-2) is too small, the impact strength of the three-dimensional modeled object obtained by optical modeling becomes small, and the toughness of the three-dimensional modeled object tends to decrease, and the three-dimensional model The yellowness of the shaped article increases and the light transmittance tends to decrease.
On the other hand, if the content of polyalkylene glycol mono (meth) acrylate (A-1) is too large, the flexibility of the three-dimensional structure obtained by optical modeling becomes excessive, and the heat resistance and rigidity of the three-dimensional structure decrease. In addition, the absorption rate of moisture and moisture is increased and the dimensional stability is lowered.

The resin composition for optical three-dimensional modeling of the present invention includes a polyalkylene glycol di (meth) acrylate (B-1) and a polyalkylene glycol mono (meth) acrylate (B-2) as the radical polymerizable organic compound (B). In addition, other radical polymerizable organic compounds can be contained.
As other radical polymerizable organic compounds, it is used in a resin composition for optical three-dimensional modeling other than polyalkylene glycol di (meth) acrylate (B-1) and polyalkylene glycol mono (meth) acrylate (B-2). Any radically polymerizable organic compound can be used.
Representative examples of other radical polymerizable organic compounds have a (meth) acrylate group other than polyalkylene glycol di (meth) acrylate (B-1) and polyalkylene glycol mono (meth) acrylate (B-2). Examples include compounds, unsaturated polyester compounds, allylurethane compounds, polythiol compounds, and the like, and one or more of these radical polymerizable organic compounds can be used.

  Among them, as the other radical polymerizable organic compound, at least one per molecule other than polyalkylene glycol di (meth) acrylate (B-1) and polyalkylene glycol mono (meth) acrylate (B-2) is used. A compound having a (meth) acryloyloxy group is preferably used. Specific examples thereof include (meth) acrylic acid esters of alcohols other than polyalkylene glycol di (meth) acrylate (B-1) and polyalkylene glycol mono (meth) acrylate (B-2), epoxy compounds and (meta ) Reaction products with acrylic acid, urethane (meth) acrylate, polyester (meth) acrylate, polyether (meth) acrylate, and the like.

Examples of the (meth) acrylic acid esters of the above-mentioned alcohols that can be used as other radical polymerizable organic compounds include aromatic alcohols, aliphatic alcohols, alicyclic alcohols having at least one hydroxyl group in the molecule, and / or The (meth) acrylate obtained by reaction with those alkylene oxide adducts and (meth) acrylic acid etc. can be mentioned.
More specifically, (meth) acrylic acid esters of alcohols include bisphenol compounds such as bisphenol A and bisphenol S or bisphenol compounds such as bisphenol A and bisphenol S in which the benzene ring is substituted with an alkoxy group. (Meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isooctyl (meth) acrylate, tetrahydro Furfuryl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, ethylene glycol di (meth) acrylate, propylene glycol di ( ) Acrylate, 1,4-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra Multivalents having three or more hydroxyl groups such as (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. Examples include poly (meth) acrylates of alcohols, (meth) acrylates of alkylene oxide adducts of polyhydric alcohols such as diols, triols, tetraols, and hexaols described above. It can be.

  Moreover, as a reaction product of an above-mentioned epoxy compound and (meth) acrylic acid, it is obtained by reaction with an aromatic epoxy compound, an alicyclic epoxy compound, and / or an aliphatic epoxy compound, and (meth) acrylic acid. Specific examples include (meth) acrylate-based reaction products. Specific examples include bisphenol compounds such as bisphenol A and bisphenol S, bisphenol compounds such as bisphenol A and bisphenol S in which the benzene ring is substituted with an alkoxy group, or the like. A (meth) acrylate obtained by reacting a glycidyl ether obtained by the reaction of an alkylene oxide adduct of the bisphenol compound or substituted bisphenol compound with an epoxidizing agent such as epichlorohydrin with (meth) acrylic acid. , And the like epoxy novolac resin and (meth) obtained by reacting acrylic acid (meth) acrylate reaction product.

  Examples of the urethane (meth) acrylate described above include (meth) acrylate obtained by reacting a hydroxyl group-containing (meth) acrylic acid ester with an isocyanate compound. As the hydroxyl group-containing (meth) acrylic acid ester, a hydroxyl group-containing (meth) acrylic acid ester obtained by an esterification reaction of an aliphatic dihydric alcohol and (meth) acrylic acid is preferable. As a specific example, 2-hydroxy Examples thereof include ethyl (meth) acrylate. Moreover, as said isocyanate compound, the polyisocyanate compound which has a 2 or more isocyanate group in 1 molecule like tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate etc. is preferable.

Furthermore, examples of the polyester (meth) acrylate described above include polyester (meth) acrylate obtained by a reaction between a hydroxyl group-containing polyester and (meth) acrylic acid.
Moreover, as above-mentioned polyether (meth) acrylate, the polyether acrylate obtained by reaction of a hydroxyl-containing polyether and acrylic acid can be mentioned.

Among them, in the resin composition for optical three-dimensional modeling of the present invention, as other radical polymerizable organic compounds, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meta) ) One of compounds having three or more (meth) acrylate groups, such as acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. It is preferable to contain 2 or more types, and thereby, the heat deformation temperature of the three-dimensional structure obtained by optical modeling becomes higher, and the heat resistance is further improved.
When the resin composition for optical three-dimensional modeling of the present invention contains a compound having three or more (meth) acrylate groups as another radical polymerizable organic compound, the content ratio is a radical polymerizable organic compound. Based on the total mass of (B), it is preferably 70% by mass or less, and more preferably 20 to 60% by mass. When the content ratio of the compound having three or more (meth) acrylate groups is too large, the toughness and flexibility of the three-dimensional structure are lowered, and the light transmittance and the color tone are liable to be lowered.

In the present invention, as the cationic polymerization initiator (C), any polymerization initiator capable of initiating cationic polymerization of the cationic polymerizable organic compound (A) when irradiated with active energy rays such as light can be used. Among them, as the cationic polymerization initiator (C), an onium salt that releases a Lewis acid when irradiated with active energy rays is preferably used. Examples of such an onium salt include an aromatic sulfonium salt of a Group VIIa element, an aromatic onium salt of a Group VIa element, an aromatic onium salt of a Group Va element, and the like.
As a typical example, a general formula: [(R ¹¹ ) (R ¹² ) (R ¹³ ) S ⁺ ] [wherein R ¹¹ , R ¹² and R ¹³ are each independently monovalent bonded to sulfur (S). Or an organic group of the general formula: [(R ¹⁴ ) (R ¹⁵ ) I ⁺ ] [wherein R ¹⁴ and R ¹⁵ are each independently a monovalent group bonded to iodine (I). An iodonium ion represented by an organic group] is represented by a general formula: [(Rf) _m PF _6-m ⁻ ] (wherein Rf is a fluoroalkyl group, m is an integer of 0 to 6) ( Phosphate ion), an anion (antimonate ion) represented by the general formula: [(Rf) _n SbF _6-n ⁻ ] (wherein Rf is a fluoroalkyl group, n is an integer of 0 to 6), [BF ₄ ^-] represented by anions, wherein: [AsF ₆ ^-], such as the anion represented by the bound cationic polymerization open Or the like can be mentioned agents.

  Although it is not limited at all, more specifically, as the cationic polymerization initiator (C), for example, a phosphorus-based sulfonium compound (C-1) represented by the following general formula (C-1), An antimony sulfonium compound (C-2) represented by the following general formula (C-2) can be exemplified.

［上記の一般式（Ｃ−１）および（Ｃ−２）中、Ｒ⁹、Ｒ¹⁰およびＲ¹¹は１価の有機基、Ｒｆはフルオロアルキル基、ｍおよびｎは０〜６の整数、ｐは上記の一般式（Ｃ−１）における「カチオン［Ｓ⁺（Ｒ⁹）（Ｒ¹⁰）（Ｒ¹¹）］が有する陽イオン価と同じ数、ｑは上記の一般式（Ｃ−２）における「カチオン［Ｓ⁺（Ｒ⁹）（Ｒ¹⁰）（Ｒ¹¹）］が有する陽イオン価と同じ数である。］

[In the above general formulas (C-1) and (C-2), R ⁹ , R ¹⁰ and R ¹¹ are monovalent organic groups, Rf is a fluoroalkyl group, m and n are integers of 0 to 6, p Is the same number as the cation number of “cation [S ⁺ (R ⁹ ) (R ¹⁰ ) (R ¹¹ )]” in general formula (C-1), q is the same as in general formula (C-2) “The number is the same as the cation number of the cation [S ⁺ (R ⁹ ) (R ¹⁰ ) (R ¹¹ )].”

In the phosphorus-based sulfonium compound (C-1) and antimony-based sulfonium compound (C-2) represented by the above general formula, typical examples of R ⁹ , R ¹⁰ and R ¹¹ are the following formulas << 1 >> to The group shown by << 11 >> can be mentioned.

［式中、Ｒ¹²、Ｒ¹³、Ｒ¹⁴、Ｒ¹⁵、Ｒ¹⁶、Ｒ¹⁷、Ｒ¹⁸、Ｒ¹⁹、Ｒ²⁰、Ｒ²¹、Ｒ²²およびＲ²³は、それぞれ独立して、置換基を有していてもよいアルキル基またはアリール基であり、Ｘ¹、Ｘ²、Ｘ³、Ｘ⁴、Ｘ⁵、Ｘ⁶、Ｘ⁷、Ｘ⁸、Ｘ⁹、Ｘ¹⁰、Ｘ¹¹、Ｘ¹²、Ｘ¹³、Ｘ¹⁴、Ｘ¹⁵、Ｘ¹⁶、Ｘ¹⁷、Ｘ¹⁸、Ｘ¹⁹、Ｘ²⁰、Ｘ²¹およびＸ²²は、それぞれ独立して、アルキル基、アリール基、アルコキシ基、アリールオキシ基、ヒドロキシ（ポリ）アルキレンオキシ基、水酸基、シアノ基、ニトロ基およびハロゲン原子から選ばれる基であり、Ｚ¹、Ｚ²、Ｚ³およびＺ⁴は、それぞれ独立して、式：−Ｓ−、−ＳＯ−および−Ｏ−から選ばれる２価の基であり、それぞれ独立して、ｄ¹は０〜５の整数、ｄ²、ｄ³およびｄ⁴は０〜４の整数、ｄ⁵は０〜５の整数、ｄ⁶、ｄ⁷、ｄ⁸、ｄ⁹、ｄ¹⁰、ｄ¹¹、ｄ¹²、ｄ¹³、ｄ¹⁴、ｄ¹⁵およびｄ¹⁶は０〜４の整数、ｄ¹⁷は０〜５の整数、ｄ¹⁸は０〜４の整数、ｄ¹⁹は０〜５の整数、ｄ²⁰、ｄ²¹およびｄ²²は０〜４の整数である。］

[Wherein R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² and R ²³ each independently have a substituent. An alkyl group or an aryl group which may be X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ , X ⁹ , X ¹⁰ , X ¹¹ , X ¹² , X ¹³ , X ¹⁴ , X ¹⁵ , X ¹⁶ , X ¹⁷ , X ¹⁸ , X ¹⁹ , X ²⁰ , X ²¹ and X ²² are each independently an alkyl group, aryl group, alkoxy group, aryloxy group, hydroxy ( A poly) alkyleneoxy group, a hydroxyl group, a cyano group, a nitro group and a halogen atom, and Z ¹ , Z ² , Z ³ and Z ⁴ are each independently a group represented by the formula: —S—, —SO—. and a divalent group selected from -O-, each independently, d ¹ is an integer of 0~5, d ^2, d ³ and d ⁴ are integers of 0 to 4 Number, d ⁵ is an integer of ^{0~5, d 6, d 7,} d 8, d 9, d 10, d 11, d 12, d 13, d 14, d 15 and d ¹⁶ are an integer of 0 to 4, d ¹⁷ is an integer of 0 to 5, d ¹⁸ is an integer of 0 to 4, d ¹⁹ is an integer of 0 to 5, d ^20, d ²¹ and d ²² represents an integer of 0-4. ]

  Although not limited at all, specific examples of the phosphorus-based sulfonium compound (C-1) represented by the above general formula include triphenylsulfonium tris (perfluoroethyl) trifluorophosphate, the following formula (C -1α) (“CPI-500K” manufactured by San Apro Co., Ltd.), a compound represented by the following formula (C-1β) (“CPI-500P” manufactured by San Apro Co., Ltd.), and the following formula (C −1γ) (“CPI-200K” manufactured by San Apro Co., Ltd.), 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluorophosphate) (ADEKA Corporation) Manufactured "SP-152").

  Specific examples of the antimony sulfonium compound (C-2) represented by the above general formula include bis- [4- (monophenylsulfonio) phenyl] sulfide bismonohexafluoroantimonate, bis- [ 4- (mono-4′-hydroxyethoxyphenylsulfonio) phenyl] sulfide bismonohexafluoroantimonate, 4- (phenylthio) phenylmonophenylsulfonium hexafluoroantimonate represented by the following formula (C-2α) (“CPI-101A” or “CPI-110S” manufactured by San Apro Co., Ltd.), 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate) (ADEKA Corporation) "SP-172" manufactured) It is possible.

In the present invention, one or more of the above cationic polymerization initiators can be used. Among them, aromatic sulfonium salts are more preferably used in the present invention.
In the present invention, for the purpose of improving the reaction rate, a photosensitizer such as benzophenone, alkoxyanthracene, monoalkoxyanthracene, thioxanthone and the like may be used together with the cationic polymerization initiator (C) as necessary.

  As the radical polymerization initiator (D), any polymerization initiator capable of initiating radical polymerization of the radical polymerizable organic compound (B) when irradiated with an active energy ray such as light can be used. Examples thereof include monoalkyl acetal compounds, phenyl ketone compounds, acetophenone compounds, benzoin or alkyl ether compounds thereof, benzophenone compounds, and thioxanthone compounds.

Specifically, examples of benmonol or a monoalkyl acetal compound thereof include benmonol monomethyl ketal and benmonol-β-methoxyethyl acetal.
Examples of the phenyl ketone compound include 1-hydroxy-cyclohexyl phenyl ketone.
Examples of the acetophenone compound include monoethoxyacetophenone, 2-hydroxymethyl-1-phenylpropan-1-one, 4′-isopropyl-2-hydroxy-2-methyl-propiophenone, and 2-hydroxy-2. -Methyl-propiophenone, p-monomethylaminoacetophenone, p-tert-butylmonochloroacetophenone, p-tert-butyltrichloroacetophenone, p-ammonodobenzalacetophenone and the like.

Examples of benzoin compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin normal butyl ether, and benzoin isobutyl ether.
Examples of the benzophenone compounds include benzophenone, methyl o-benzoylbenzoate, Michler's ketone, 4,4′-bismonoethylaminobenzophenone, 4,4′-monochlorobenzophenone, and the like.
Examples of the thioxanthone compound include thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, and 2-isopropylthioxanthone.

In this invention, 1 type, or 2 or more types of radical polymerization initiator (D) can be mix | blended and used according to desired performance.
Among them, in the present invention, 1-hydroxycyclohexyl phenyl ketone is preferably used as the radical polymerization initiator (D) from the viewpoint that the three-dimensional modeled product obtained by optical modeling has a small yellowness and a good hue. .

  The resin composition for optical three-dimensional modeling of the present invention includes the viscosity of the composition, the reaction rate, the modeling speed, the toughness of the three-dimensional modeled product, impact resistance, durability, heat distortion temperature (heat resistance), dimensional accuracy, From the viewpoint of mechanical properties and the like, based on the total mass of the resin composition for optical three-dimensional modeling, the cationically polymerizable organic compound (A) is 30 to 85% by mass, further 40 to 80% by mass, particularly 45 to 75%. It is contained in a proportion of 10% by mass, the radical polymerizable organic compound (B) is contained in a proportion of 10 to 50% by mass, further 15 to 45% by mass, particularly 20 to 40% by mass, and the cationic polymerization initiator (C) In an amount of 0.1 to 10% by mass, more preferably 0.5 to 8% by mass, particularly 1 to 5% by mass, and 0.1 to 10% by mass of radical polymerization initiator (D). It is preferable to contain in the ratio of 5-8 mass%, especially 1-4 mass%.

  Moreover, the resin composition for optical three-dimensional model | molding of this invention may contain the polyalkylene glycol and the etherified product of the polyalkylene glycol which etherified the hydroxyl group of the one terminal or both ends as needed. By including the polyalkylene glycol and / or the etherified product of polyalkylene glycol obtained by etherifying the terminal hydroxyl group, the impact strength of the three-dimensional structure obtained by optical modeling is improved.

Examples of the etherified product of polyalkylene glycol and / or polyalkylene glycol obtained by etherifying a terminal hydroxyl group can be contained in the resin composition for optical three-dimensional modeling of the present invention include polyethylene glycol, polypropylene glycol, poly (oxyethylene / Oxypropylene random copolymer) diol, polyoxyethylene polymer block / polyoxypropylene polymer block-bonded block copolymer having hydroxyl groups at both ends (block copolymer diol), polytetramethylene glycol, ethylene oxide unit Random copolymer diol, polyoxyethylene polymer block / polytetramethylene glycol polymer block having hydroxyl groups at both ends and tetramethylene oxide units bonded at random. Examples include block copolymers having hydroxyl groups at both ends (block copolymer diols), etherified products in which the hydroxyl groups at one or both ends of these diols are etherified with alkyl groups, cycloalkyl groups, aryl groups, or the like. it can.
Among them, polyethylene glycol, since it is easy to obtain, is liquid at room temperature, has excellent handleability, and a molded product obtained from an optical three-dimensional model has excellent transparency, flexibility, toughness, and durability. One or more of polypropylene glycol and polytetramethylene glycol are preferably used, and polytetramethylene glycol is more preferably used.

  The average molecular weight of the polyalkylene glycol and the etherified product thereof is preferably 200 to 4000, more preferably 300 to 2000, and further preferably 400 to 1000. From the standpoints of various properties such as solubility, miscibility, and photocuring of the three-dimensional structure obtained by photocuring, such as impact strength, toughness, and durability, in the optical three-dimensional structure resin composition described above. The average molecular weight of the polyalkylene glycol and its terminal hydroxyl group etherified product is preferably 500 to 1000, more preferably 600 to 900.

  The content ratio of the polyalkylene glycol and / or the polyalkylene glycol etherified product obtained by etherifying the terminal hydroxyl group is preferably 0 to 10% by mass based on the total mass of the resin composition for optical three-dimensional modeling, and the content ratio If the amount is too large, a decrease in photocurability, a decrease in heat deformation temperature of a three-dimensional structure obtained by optical modeling, a decrease in heat resistance associated therewith, a decrease in transparency, and the like are caused.

  As long as the effect of the present invention is not impaired, the resin composition for optical three-dimensional modeling of the present invention includes, as necessary, a colorant such as a dye, an antifoaming agent, a leveling agent, a thickener, a flame retardant, and an antioxidant. Further, it may contain an appropriate amount of one type or two or more types such as a modifying resin.

Any of the conventionally known optical three-dimensional modeling methods and apparatuses can be used for optical three-dimensional modeling using the optical modeling resin composition of the present invention. As a representative example of the optical three-dimensional modeling method that can be preferably adopted, the active energy ray is selectively irradiated so that a cured layer having a desired pattern is obtained in the liquid resin composition for optical modeling of the present invention. Then, a cured layer is formed, and then an uncured liquid optical modeling resin composition is supplied to the cured layer, and similarly, a cured layer continuous with the cured layer is formed by irradiating active energy rays. The method of finally obtaining the target three-dimensional molded item can be mentioned by repeating lamination | stacking operation.
Examples of the active energy rays at that time include ultraviolet rays, electron beams, X-rays, radiation, and high frequencies as described above. Among them, ultraviolet rays having a wavelength of 300 to 400 nm are preferably used from an economical viewpoint, and as a light source at that time, an ultraviolet laser (for example, a semiconductor-excited solid laser, an Ar laser, a He—Cd laser), a high-pressure mercury lamp is used. Ultra high pressure mercury lamps, low pressure mercury lamps, xenon lamps, halogen lamps, metal halide lamps, ultraviolet LEDs (light emitting diodes), ultraviolet fluorescent lamps, and the like can be used.

  When forming a cured resin layer having a predetermined shape pattern by irradiating an active energy ray on a modeling surface made of a resin composition for optical three-dimensional modeling, the active energy is reduced to a point such as a laser beam. A hardened resin layer may be formed by using a line in a stippling or line drawing method, or a planar drawing formed by arranging a plurality of micro light shutters such as a liquid crystal shutter or a demonotal micromirror shutter (DMD). You may employ | adopt the shaping | molding system which irradiates a shaping | molding surface to a shaping | molding surface through a mask in a planar shape, and forms a cured resin layer.

  The resin composition for optical modeling of the present invention can be widely used in the field of optical three-dimensional modeling, and is not limited at all. However, as a typical application field, the appearance design is verified during the design. Shape confirmation model, functional test model for checking the functionality of parts, master model for producing mold, master model for producing mold, direct mold for prototype mold, automobile and motorcycle Lenses, restoration of art, imitation and contemporary art, art and craft fields such as design presentation models for glass-walled buildings, precision parts, electrical and electronic parts, furniture, building structures, automotive parts, various containers, It can be effectively used for applications such as models such as castings, mother dies, and processing.

The three-dimensional object obtained by optical modeling of the resin composition for optical three-dimensional modeling of the present invention has a high heat deformation temperature and heat resistance compared to the conventional optical three-dimensional model even without heat treatment after the optical modeling. Therefore, it can be used as it is without being subjected to heat treatment.
And since the three-dimensional molded article obtained by performing optical modeling using the resin composition for optical three-dimensional modeling of the present invention has a higher heat distortion temperature and is more excellent in heat resistance when subjected to heat treatment. When a three-dimensional structure that is more excellent in heat resistance is required, the three-dimensional structure obtained by using the optical three-dimensional resin composition of the present invention is heat-treated to obtain a three-dimensional structure that has improved heat resistance. Good.
The heat treatment for further increasing the thermal deformation temperature of the three-dimensional structure is preferably performed at a temperature of 50 ° C. or higher, more preferably at a temperature of 60 to 150 ° C., and preferably at a temperature of 80 to 120 ° C. Further preferred. When heat-treating at a temperature of 100 ° C. or higher, without first heating to 100 ° C. or higher, the temperature is first preheated to a temperature lower than 100 ° C. (eg, a temperature of about 40 to 60 ° C.) and then 100 ° C. or higher When heated at, it is possible to effectively prevent dimensional changes and deformation of the three-dimensional structure.
The heat treatment can be performed by a method of heating a three-dimensional structure obtained by optical modeling in a heating chamber, a method of heating with a heat medium such as silicone oil, or the like.
The heat treatment after stereolithography is effective for manufacturing prototypes such as automobile engine parts that require high heat resistance.

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the examples.
In the following examples, the viscosity of the resin composition for optical three-dimensional modeling, the mechanical properties of the optical molding obtained by optical modeling using the resin composition for optical modeling [tensile properties (tensile strength (tensile strength, tensile elongation, Tensile modulus), bending properties (bending strength, flexural modulus), impact strength], heat distortion temperature, yellowness and total light transmittance were measured as follows.

(1) Viscosity of the resin composition for optical three-dimensional modeling:
After adjusting the temperature of the resin composition for optical three-dimensional modeling to 25 ° C. in a thermostatic bath at 25 ° C., it was measured using a B-type viscometer (manufactured by Tokyo Keiki Co., Ltd.).

(2) Tensile characteristics (tensile strength, tensile elongation, tensile modulus) of stereolithography:
Stereolithography manufactured in the following examples or comparative examples (test pieces having a dumbbell shape in accordance with JIS K-7113) (stereolithography before heat treatment and stereolithography subjected to heat treatment at 100 ° C. for 120 minutes) The tensile strength, tensile elongation and tensile modulus of the test piece were measured according to JIS K-7113.

(3) Bending characteristics (bending strength, bending elastic modulus) of the optically shaped object:
The bending strength and the flexural modulus of the test piece were measured according to JIS K-7171 using the optically shaped article (bar-shaped test piece conforming to JIS K-7171) produced in the following examples or comparative examples. .

(4) Impact strength of stereolithography:
Stereolithography manufactured in the following examples or comparative examples (test pieces with notches in accordance with JIS K-7110) (prefabricated stereolithography before heat treatment and preheating at 50 ° C for 1 hour, then at 100 ° C for 120 minutes Using a digital impact tester “Model DG-18” manufactured by Toyo Seiki Co., Ltd. and measuring the Izod impact strength with a notch according to JIS K-7110. did.

(5) Thermal deformation temperature of stereolithography:
Stereolithography manufactured in the following examples or comparative examples (bar-shaped test piece according to JIS K-7171) (stereolithography before heat treatment and stereolithography subjected to heat treatment at 100 ° C. for 120 minutes) Using a “HDT tester 6M-2” manufactured by Toyo Seiki Co., Ltd., applying a load of 1.81 MPa to the test piece, the heat deformation temperature of the test piece in accordance with JIS K-7207 (Method A) Further, a load of 0.45 MPa was applied to the test piece, and the thermal deformation temperature of the test piece was measured according to JIS K-7207 (Method B).

(6) Yellowness of stereolithography:
Stereolithography manufactured in the following examples or comparative examples [cube test piece having a width of 20 mm, a height of 45 mm, and a thickness of 10 mm (measurement surface)] (the stereolithography before heat treatment and after preheating at 50 ° C. for 1 hour Specified in JISK7373 by color analysis using an ultraviolet-visible spectrophotometer “U-3900H” manufactured by Hitachi High-Technology Co., Ltd. and an integrating sphere. The standard illuminant D65 and the yellow index (YI) with respect to the 2-degree field of view were determined to determine the yellowness of the stereolithography.

(7) Total light transmittance of stereolithography:
Stereolithography polyepoxy compound produced in the following examples or comparative examples [cube specimen having a width of 20 mm, a height of 45 mm, and a thickness of 10 mm (measurement surface)] Using a UV-visible spectrophotometer “UV-3900H” and an integrating sphere manufactured by Hitachi High-Technologies Corporation, a standard illuminant D65 was used. The spectral transmittance with respect to a 2 degree visual field was measured, and the total light transmittance defined in JIS R-3106 was determined.

Example 1
(1) 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [1,1-bis [4-([2,3-epoxypropoxy] phenyl] ethyl] phenyl] propane ( 24 parts by mass of the above-described VG3101L (hereinafter referred to as “VG3101L”), 14 parts by mass of hydrogenated bisphenol A monoglycidyl ether (“HBE-100” manufactured by Shin Nippon Chemical Co., Ltd.), 3,4-epoxycyclohexylmethyl-3 ′, 10 parts by mass of 4′-epoxycyclohexanecarboxylate (“Celoxide 2021P” manufactured by Daicel Corporation), polytetramethylene glycol diglycidyl ether (“Epogosei PT” manufactured by Yokkaichi Chemical Co., Ltd.), the number of bonds of tetramethylene oxide units≈9, Average molecular weight ≈ 780) 6 parts by mass, 3-ethyl-3-hydroxymethyl 6 parts by mass of oxetane (“OXT-101” manufactured by Toagosei Co., Ltd.), 12 parts by mass of bis (3-ethyl-3-oxetanylmethyl) ether (“OXT-221” manufactured by Toagosei Co., Ltd.), dipentaerythritol polyacrylate ("A-9550" manufactured by Shin-Nakamura Chemical Co., Ltd., mixture of pentaacrylate and hexaacrylate) 12 parts by mass, polytetramethylene glycol diacrylate (Kyoeisha Chemical Co., Ltd. "FA-PTG9A", number of bonds of tetramethylene oxide units) ≈ 9, average molecular weight ≈ 770) 7 parts by weight, polypropylene glycol monoacrylate (Nippon Yushi Co., Ltd. “Blenmer AP150”, number of bonds of propylene oxide unit ≈ 3, average molecular weight ≈ 150) 4 parts by weight, cationic polymerization initiator ( "CPI-20" made by Sun Apro Co., Ltd. K ") 3 parts by mass of 1-hydroxy - cyclohexyl phenyl ketone (BASF Corp." Irgacure 184 ") (to prepare a radical polymerization initiator) 2 parts by weight was mixed well for stereolithography resin composition.
It was 610 mPa * s (25 degreeC) when the viscosity of this resin composition for optical three-dimensional modeling was measured by the above-mentioned method.

(2) Using the resin composition for optical three-dimensional modeling obtained in (1) above, a semiconductor laser (rated output 200 mW; wavelength) using an ultra-high-speed optical modeling system (“SOLIFORM250” manufactured by Nabtesco Corporation) 355 nm; manufactured by SpectraFimonox), under the condition of a liquid surface irradiation energy of 100 mJ / cm ² , an optical three-dimensional modeling is performed with a slice pitch (lamination thickness) of 0.10 mm and an average modeling time of 2 minutes per layer. , Test pieces for measuring physical properties (dumbbell-shaped test pieces according to JIS K-7113, bar-shaped test pieces according to JIS K-7171, Izod impact test pieces according to JIS K-7110), A 10 mm thick test piece for measuring the yellowness and the total light transmittance was prepared. The obtained test piece was post-cured by irradiation with ultraviolet rays (metal halide lamp, wavelength 365 nm, intensity 3.0 mW / cm ² ) for 20 minutes.
The mechanical properties, heat distortion temperature, yellowness, and total light transmittance of the post-cured test piece (test piece before heat treatment) were measured by the methods described above, and as shown in Table 1 below.
(3) The test piece (test piece post-cured with ultraviolet rays) obtained in (2) above is placed in a thermostatic bath at a temperature of 50 ° C., preheated for 1 hour, and then heat-treated at 100 ° C. for 120 minutes, and then the thermostatic bath And then left at room temperature (25 ° C.) for 24 hours, and then the mechanical properties, thermal deformation temperature, yellowness and total light transmittance of the test piece were measured by the methods described above, as shown in Table 1 below. Met.

Example 2
(1) Implementation except that the amount of hydrogenated bisphenol A monoglycidyl ether (HBE-100) was changed to 12 parts by mass and the amount of polytetramethylene glycol diglycidyl ether (Epogosei PT) was changed to 8 parts by mass A resin composition for optical three-dimensional modeling was prepared in the same manner as in Example 1 (1).
It was 512 mPa * s (25 degreeC) when the viscosity of this resin composition for optical three-dimensional modeling was measured by the above-mentioned method.
(2) Using the resin composition for optical three-dimensional modeling obtained in (1) above, a test piece for measuring physical properties was prepared in the same manner as in (2) of Example 1, and the obtained test piece was used. The film was post-cured by irradiation with ultraviolet rays (metal halide lamp, wavelength 365 nm, intensity 3.0 mW / cm ² ) for 20 minutes.
The mechanical properties, heat distortion temperature, yellowness, total light transmittance and water absorption of the post-cured test piece (test piece before heat treatment) were measured by the methods described above, and as shown in Table 1 below. It was.
(3) The test piece (test piece post-cured with ultraviolet rays) obtained in (2) above is placed in a thermostatic bath at a temperature of 50 ° C., preheated for 1 hour, and then heat-treated at 100 ° C. for 120 minutes, and then the thermostatic bath And then left at room temperature (25 ° C.) for 24 hours, and then the mechanical properties, thermal deformation temperature, yellowness and total light transmittance of the test piece were measured by the methods described above, as shown in Table 1 below. Met.

Example 3
(1) 24 parts by mass of VG3101L, 9 parts by mass of hydrogenated bisphenol A monoglycidyl ether (“HBE-100” manufactured by Shin Nippon Rika Co., Ltd.), 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxy Rate (Celoxide 2021P) 10 parts by mass, Polytetramethylene glycol diglycidyl ether (Epogosei PT) 7 parts by mass, 3-ethyl-3-hydroxymethyloxetane (OXT-101) 5 parts by mass, bis (3-ethyl-3- Oxetanylmethyl) ether (OXT-221) 12 parts by mass, dipentaerythritol polyacrylate (A-9550) 12 parts by mass, polytetramethylene glycol diacrylate (FA-PTG9A) 7 parts by mass, polypropylene glycol monoacrylate 2 parts by mass of bisphenol A diglycidyl ether ("VR77" made by Showa Denko KK), polytetramethylene glycol ("PTG-850SN" made by Hodogaya Chemical Co., Ltd.) , Average molecular weight ≈ 850) 3 parts by weight, 3 parts by weight of a cationic polymerization initiator (CPI-200K) and 2 parts by weight of 1-hydroxy-cyclohexyl phenyl ketone (Irgacure 184) (radical polymerization initiator) A resin composition for three-dimensional modeling was prepared.
It was 584 mPa * s (25 degreeC) when the viscosity of this resin composition for optical three-dimensional modeling was measured by the above-mentioned method.
(2) Using the resin composition for optical three-dimensional modeling obtained in (1) above, a test piece for measuring physical properties was prepared in the same manner as in (2) of Example 1, and the obtained test piece was used. The film was post-cured by irradiation with ultraviolet rays (metal halide lamp, wavelength 365 nm, intensity 3.0 mW / cm ² ) for 20 minutes.
The mechanical properties, heat distortion temperature, yellowness, total light transmittance and water absorption of the post-cured test piece (test piece before heat treatment) were measured by the methods described above, and as shown in Table 1 below. It was.
(3) The test piece (test piece post-cured with ultraviolet rays) obtained in (2) above is placed in a thermostatic bath at a temperature of 50 ° C., preheated for 1 hour, and then heat-treated at 100 ° C. for 120 minutes, and then the thermostatic bath And then left at room temperature (25 ° C.) for 24 hours, and then the mechanical properties, thermal deformation temperature, yellowness and total light transmittance of the test piece were measured by the methods described above, as shown in Table 1 below. Met.

Example 4
(1) 24 parts by mass of VG3101L, 13 parts by mass of hydrogenated bisphenol A monoglycidyl ether (“HBE-100” manufactured by Shin Nippon Rika Co., Ltd.), 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxy Rate (Celoxide 2021P) 10 parts by mass, polytetramethylene glycol diglycidyl ether (Epogosei PT) 4 parts by mass, 3-ethyl-3-hydroxymethyloxetane (OXT-101) 5 parts by mass, bis (3-ethyl-3- Oxetanylmethyl) ether (OXT-221) 12 parts by mass, dipentaerythritol polyacrylate (A-9550) 6 parts by mass, polytetramethylene glycol diacrylate (FA-PTG9A) 7 parts by mass, polypropylene glycol monoacrylate Nmer AP150) 4 parts by weight, bisphenol A diglycidyl ether acrylic acid 2 mole adduct (VR77) 6 parts by weight, polytetramethylene glycol (PTG-850SN) 4 parts by weight, cationic polymerization initiator (CPI-200K) 3 parts by weight Part and 1 part of 1-hydroxy-cyclohexyl phenyl ketone (Irgacure 184) (radical polymerization initiator) were mixed well to prepare a resin composition for optical three-dimensional modeling.
It was 632 mPa * s (25 degreeC) when the viscosity of this resin composition for optical three-dimensional modeling was measured by the above-mentioned method.
(2) Using the resin composition for optical three-dimensional modeling obtained in (1) above, a test piece for measuring physical properties was prepared in the same manner as in (2) of Example 1, and the obtained test piece was used. The film was post-cured by irradiation with ultraviolet rays (metal halide lamp, wavelength 365 nm, intensity 3.0 mW / cm ² ) for 20 minutes.
The mechanical properties, heat distortion temperature, yellowness, total light transmittance and water absorption of the post-cured test piece (test piece before heat treatment) were measured by the methods described above, and as shown in Table 2 below. It was.
(3) The test piece (test piece post-cured with ultraviolet rays) obtained in the above (2) is put in a thermostatic bath at a temperature of 100 ° C. and heat-treated for 120 minutes, and then taken out from the thermostatic bath at room temperature (25 ° C.). After being allowed to stand for 24 hours, the mechanical properties, heat distortion temperature, yellowness and total light transmittance of the test piece were measured by the methods described above, and as shown in Table 2 below.

Example 5
(1) In Example 1, (1), instead of 4 parts by mass of polypropylene glycol monoacrylate (Blemmer AP150), 4 parts by mass of polypropylene glycol monoacrylate (“Blemmer AP250” manufactured by NOF Corporation, average molecular weight≈250) A resin composition for optical three-dimensional modeling was prepared in the same manner as (1) of Example 4 except that was used.
It was 690 mPa * s (25 degreeC) when the viscosity of this resin composition for optical three-dimensional modeling was measured by the above-mentioned method.
(2) Using the resin composition for optical three-dimensional modeling obtained in (1) above, a test piece for measuring physical properties was prepared in the same manner as in (2) of Example 1, and the obtained test piece was used. The film was post-cured by irradiation with ultraviolet rays (metal halide lamp, wavelength 365 nm, intensity 3.0 mW / cm ² ) for 20 minutes.
The mechanical properties, heat distortion temperature, yellowness, total light transmittance and water absorption of the post-cured test piece (test piece before heat treatment) were measured by the methods described above, and as shown in Table 2 below. It was.
(3) The test piece (test piece post-cured with ultraviolet rays) obtained in the above (2) is put in a thermostatic bath at a temperature of 100 ° C. and heat-treated for 120 minutes, and then taken out from the thermostatic bath at room temperature (25 ° C.). After being allowed to stand for 24 hours, the mechanical properties, heat distortion temperature, yellowness and total light transmittance of the test piece were measured by the methods described above, and as shown in Table 2 below.

<< Comparative Example 1 >>
(1) 24 parts by mass of VG3101L, 26 parts by mass of hydrogenated bisphenol A monoglycidyl ether (“HBE-100” manufactured by Shin Nippon Chemical Co., Ltd.), 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxy Rate (Celoxide 2021P) 10 parts by mass, 3-ethyl-3-hydroxymethyloxetane (OXT-101) 5 parts by mass, bis (3-ethyl-3-oxetanylmethyl) ether (OXT-221) 12 parts by mass, dipenta Erythritol polyacrylate (A-9550) 12 parts by mass, lauryl acrylate 6 parts by mass, cationic polymerization initiator (CPI-200K) 3 parts by mass, and 1-hydroxy-cyclohexyl phenyl ketone (Irgacure 184) (radical polymerization initiator) 2 parts by mass Mix well The biological stereolithography resin composition was prepared.
It was 580 mPa * s (25 degreeC) when the viscosity of this resin composition for optical three-dimensional modeling was measured by the above-mentioned method.
(2) Using the resin composition for optical three-dimensional modeling obtained in (1) above, a test piece for measuring physical properties was prepared in the same manner as in (2) of Example 1, and the obtained test piece was used. The film was post-cured by irradiation with ultraviolet rays (metal halide lamp, wavelength 365 nm, intensity 3.0 mW / cm ² ) for 20 minutes.
The mechanical properties, heat distortion temperature, yellowness, total light transmittance and water absorption of the post-cured test piece (test piece before heat treatment) were measured by the methods described above, and as shown in Table 2 below. It was.
(3) The test piece (test piece post-cured with ultraviolet rays) obtained in (2) above is placed in a thermostatic bath at a temperature of 50 ° C., preheated for 1 hour, and then heat-treated at 100 ° C. for 120 minutes, and then the thermostatic bath And then left at room temperature (25 ° C.) for 24 hours, and then the mechanical properties, heat distortion temperature, yellowness and total light transmittance of the test piece were measured by the methods described above, as shown in Table 2 below. Met.

<< Comparative Example 2 >>
(1) 38 parts by mass of hydrogenated bisphenol A monoglycidyl ether (“HBE-100” manufactured by Shin Nippon Chemical Co., Ltd.), 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate (Celoxide 2021P) 10 Parts by mass, 6 parts by mass of polytetramethylene glycol diglycidyl ether (Epogosei PT), 12 parts by mass of 3-ethyl-3-hydroxymethyloxetane (OXT-101), bis (3-ethyl-3-oxetanylmethyl) ether (OXT) -221) 5 parts by mass, 9 parts by mass of dipentaerythritol polyacrylate (A-9550), 7 parts by mass of polytetramethylene glycol diacrylate (FA-PTG9A), 4 parts by mass of polypropylene glycol monoacrylate (Blenmer AP150) 4 parts by mass of polytetramethylene glycol (PTG-850SN), 3 parts by mass of a cationic polymerization initiator (CPI-200K) and 2 parts by mass of 1-hydroxy-cyclohexyl phenyl ketone (Irgacure 184) (radical polymerization initiator) are mixed well. Thus, a resin composition for optical three-dimensional modeling was prepared.
It was 307 mPa * s (25 degreeC) when the viscosity of this resin composition for optical three-dimensional modeling was measured by the above-mentioned method.
(2) Using the resin composition for optical three-dimensional modeling obtained in (1) above, a test piece for measuring physical properties was prepared in the same manner as in (2) of Example 1, and the obtained test piece was used. The film was post-cured by irradiation with ultraviolet rays (metal halide lamp, wavelength 365 nm, intensity 3.0 mW / cm ² ) for 20 minutes.
The mechanical properties, heat distortion temperature, yellowness, total light transmittance and water absorption of the post-cured test piece (test piece before heat treatment) were measured by the methods described above, and as shown in Table 2 below. It was.
(3) The test piece (test piece post-cured with ultraviolet rays) obtained in (2) above is placed in a thermostatic bath at a temperature of 50 ° C., preheated for 1 hour, and then heat-treated at 100 ° C. for 120 minutes, and then the thermostatic bath And then left at room temperature (25 ° C.) for 24 hours, and then the mechanical properties, heat distortion temperature, yellowness and total light transmittance of the test piece were measured by the methods described above, as shown in Table 2 below. Met.

As seen in Table 1 and Table 2 above, the resin compositions for optical three-dimensional modeling of Examples 1 to 5 are a cationic polymerizable organic compound (A), a radical polymerizable organic compound (B), and a cationic polymerization initiator. In the resin composition for optical three-dimensional modeling containing (C) and a radical polymerization initiator (D), as a part of the cationically polymerizable organic compound (A), 3 or more glycidyl etherified phenol groups in the molecule The polyalkylene glycol di (meth) acrylate (B-1) and the polyalkylene glycol diglycidyl ether (A-2) as a part of the radical polymerizable organic compound (B) Active energy rays shortened with high curing sensitivity by containing polyalkylene glycol mono (meth) acrylate (B-2) Morphism can be produced with good productivity a three-dimensional shaped object with time, is excellent in handleability upon molding at a low viscosity.
Moreover, the three-dimensional object obtained by optical modeling using the resin composition for optical three-dimensional modeling of Examples 1 to 5 has a heat deformation temperature measured under a high load of 1.81 MPa before heat treatment. The heat distortion temperature measured under a low load of 47 ° C. or higher and 0.45 MPa at the stage is 50 ° C. or higher before the heat treatment, and the heat distortion temperature is higher than usual. And the three-dimensional molded item obtained in Examples 1 to 5 has a higher heat deformation temperature by heat treatment at 100 ° C., and the heat deformation temperature rises to 62 ° C. or higher when measured under a high load. When measured under a load, the heat distortion temperature rises to 81 ° C. or higher, resulting in a three-dimensional structure that is further excellent in heat resistance.
In addition, the three-dimensional structure obtained by optical modeling using the resin composition for optical three-dimensional modeling of Examples 1 to 5 has a yellowness of 9.9 or less before heat treatment and 10.5 or less even after heat treatment. It is small and has little yellow coloration and excellent color tone. The total light transmittance is 87% or more both before and after heat treatment and excellent in transparency, and the value of impact strength is before and after heat treatment. It is as high as 24 J / m or more after heat treatment, and has excellent toughness and durability.

In contrast, the resin composition for optical three-dimensional modeling of Comparative Example 1 does not contain polyalkylene glycol diglycidyl ether (A-2) as a part of the cationically polymerizable organic compound (A), and is further a radical polymerizable organic. Since the polyalkylene glycol di (meth) acrylate (B-1) and the polyalkylene glycol mono (meth) acrylate (B-2) are not included as part of the compound (B), the yellowness value is Is 15.3 and 18.4 after heat treatment, which is higher in yellowness and poor in color than the three-dimensional objects obtained in Examples 1 to 5, and has an impact strength before heat treatment. It is as small as 15 J / m and 18 J / m after heat treatment and is inferior in toughness.
Since the resin composition for optical three-dimensional modeling of Comparative Example 2 does not contain the compound (A-1) as a part of the cationic polymerizable organic compound (A), the three-dimensional molded product obtained by optical modeling. The heat distortion temperature measured under a high load of 1.81 MPa was 44 ° C. before the heat treatment and the heat deformation temperature measured under a low load of 0.45 MPa was as low as 47 ° C. before the heat treatment. And even if the said three-dimensional molded item is heat-processed, a heat deformation temperature is 50 degrees C or less in both a high load and a low load, and the raise of a heat deformation temperature is very small.

  The resin composition for optical three-dimensional modeling of the present invention is a resin for optical three-dimensional modeling that has high curing sensitivity due to active energy rays, low viscosity, excellent handling at the time of modeling, high resolution of a modeled object, and excellent modeling accuracy. In addition to having the basic physical properties necessary for the composition, it has a high heat deformation temperature by optical modeling, has excellent heat resistance, has low yellowness and high light transmittance, and has excellent color tone and transparency, Since the three-dimensional structure excellent in mechanical properties such as impact resistance and breaking strength is given, and the heat deformation temperature is further increased by heat-treating the three-dimensional structure, the heat resistance is further improved. There is a need for a three-dimensional molded article that has high heat resistance, high transparency, good color tone, and excellent mechanical properties such as strength, elastic characteristics, impact resistance, and toughness. , A model for verifying the appearance design of various industrial products during the measurement, a model for checking the functionality of parts, a resin mold for producing molds, a base model for producing molds, automobiles and motorcycles Lenses, restoration of art, imitation and modern art, art and craft fields such as glass-based building design presentation models, precision parts, electrical and electronic parts, furniture, building structures, automotive parts, various containers It can be effectively used for various applications such as models such as castings, railways, construction machinery, industrial robots, and control parts such as airplanes.

Claims (6)

<< i >> A resin composition for optical three-dimensional modeling comprising a cationically polymerizable organic compound (A), a radically polymerizable organic compound (B), a cationic polymerization initiator (C) and a radical polymerization initiator (D) ;
<< ii >> As a part of the cationically polymerizable organic compound (A), a compound (A-1) having 3 or more glycidyl etherified phenol groups is added based on the total mass of the cationically polymerizable organic compound (A). Contained in a proportion of ˜50% by mass ;
<Iii> As part of the cationically polymerizable organic compound (A), 0.5 to 20 mass of polyalkylene glycol diglycidyl ether (A-2) based on the total mass of the cationically polymerizable organic compound (A). % Content;
<< iv >> As part of the radical polymerizable organic compound (B), the polyalkylene glycol di (meth) acrylate (B-1) is 5 to 70 mass based on the total mass of the radical polymerizable organic compound (B). % In proportion ; and
<< v >> Polyalkylene glycol mono (meth) acrylate (B-2) as part of the radical polymerizable organic compound (B) is 1 to 35 mass based on the total mass of the radical polymerizable organic compound (B). % Content;
A resin composition for optical three-dimensional modeling characterized by the above. As a part of the cationically polymerizable organic compound (A), the following general formula (A-3);

Wherein R ¹ is hydrogenated bisphenol A residue, hydrogenated bisphenol E residue, hydrogenated bisphenol F residue, hydrogenated bisphenol AD residue, hydrogenated bisphenol Z residue, cyclohexanedimethanol residue or tri Cyclodecanedimethanol residue is shown.)
In alicyclic monoglycidyl ether compound represented (A-3), claim further comprising at least one compound selected from the alicyclic epoxy compound (A-4) and the oxetane compound (A-5) 1 The resin composition for optical three-dimensional modeling described in 1. The resin for optical three-dimensional model | molding of Claim 1 or 2 which further contains the polyacryl compound (B-3) which has 3 or more of (meth) acryloyloxy groups as some radically polymerizable organic compounds (B). Composition. Based on the total mass of the resin composition for optical three-dimensional modeling, 30 to 85 mass% of the cationic polymerizable organic compound (A), 10 to 50 mass% of the radical polymerizable organic compound (B), and a cationic polymerization initiator ( The resin for optical three-dimensional modeling according to any one of claims 1 to 3 , comprising 0.1 to 10% by mass of C) and 0.1 to 10% by mass of a radical polymerization initiator (D). Composition. The method of manufacturing a three-dimensional molded item by performing an optical three-dimensional modeling using the resin composition for optical three-dimensional modeling of any one of Claims 1-4 . A three-dimensional model is manufactured by performing optical three-dimensional modeling using the resin composition for optical three-dimensional modeling according to any one of claims 1 to 4 , and a three-dimensional model obtained thereby is obtained at 50 ° C or higher. The manufacturing method of the three-dimensional molded item with improved heat resistance characterized by heat-processing at temperature.